The Total Synthesis of Natural Products (Volume 9)

THE TOTAL SYNTHESIS OF NATURAL PRODUCTS

The Total Synthesis of Natural Products VOLUME 9

Edited by

John ApSimon Ottawa-Carleton Institute for Research and Graduate Studies in Chemistry and Department of Chemistry Carleton University, Ottawa

A WILEY-INTERSCIENCE PUBLICATION

JOHN WILEY & SONS NEWYORK

CHICHESTER

BRISBANE

TORONTO

SINGAPORE

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Library of Congress Cataloging in Publication Data: The Total synthesis of natural products. “A Wiley-Interscience publication.”

Original imprint, v. 1: New York: Wiley-Interscience, 1973. Includes bibliographical references and indexes. I . Chemistry, Organic-Synthesis, I. ApSimon, John. QD262.T655 1973 541l.2 72-4075 ISBN 0-471-03251-4 (v. 1) ISBN 0-47 1-55 189-9 (v. 9)

10 9 8 7 6 5 4 3 2

I

Contributor to Volume 9 Kenji Mori, Department of Agricultural Chemistry, The University of Tokyo, Tokyo, Japan

V

Preface This volume is a single author effort covering the massive amount of synthetic work associated with Insect Pheromone Chemistry for the period 1979 to 1990. Professor Mori has, once more, demonstrated in a masterful way his key position in this field. I have been editor of this series since its inception in 1973 and, although I am convinced of its value to the discipline of organic synthesis, other responsibilities and interests have slowly intruded, to the state where I must regretfully pass on the onerous task of keeping the initiative alive to another editor. Over the past 18 years, I have had the honor of working with many outstanding authors and scientists. I thank you personally for this collaboration, friendship, and support. JOHN APSIMON Oitawa, Canada

November 1991

vii

Contents The Synthesis of Insect Pheromones, 1979-1989 KENJIMORI Subject Index

523

Formula Index

533

ix

The Total Synthesis of Natural Products, Volume9 Edited by John ApSlmon Copyright © 1992 by John Wiley & Sons, Inc.

The Synthesis of Insect Pheromones, 1979-1989 KENJI MORI Depar~menfof Agricultural Chemistry, The Universiry of Tokyo, Japan

1.

2. 3. 4. 5. 6.

7. 8. 9. 10. 11. 12. 13. 14.

15. 16.

Introduction, 2 General Methods, 3 Alkanes as Pheromones, 8 Pheromone Hydrocarbon with a Terminal Double Bond, 15 Pheromone Alcohols and Acetates with an E-Double Bond, 18 Pheromone Hydrocarbons and Acetates with a Z-Double Bond, 25 Pheromone Alcohols and Acetates with a Conjugated Diene and Conjugated Enyne System, 37 Pheromones with a Nonconjugated Diene System, 66 Phcromones with a Triene or Tetraene System, 79 Pheromones with an Epoxy Ring, 85 Chiral Alcohols and Their Esters as Pheromones, 98 Pheromone Aldehydes, 130 Pheromone Ketones, 157 Acids and Esters as Pheromones, 200 Pheromone Lactones, 2 16 lsoprenoid Hydrocarbons as Pheromones, 273 1

2

The Synthesis of Insect Pheromones, 1979-1989

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxide as Pheromones, 280 18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones, 332 19. Oxygen Heterocycles (Excluding Epoxides, Lactones, Hemiacetals, and Acetals) as Pheromones, 367 20. Acetals as Pheromones, 381 21. Spiroacetals as Pheromones, 444 22. Nitrogen Heterocycles and Sulfur-Containing Compounds as Pheromones, 478 23. Conclusion, 484 Acknowledgments, 486 References. 486

1. INTRODUCTION

Since the appearance of the first edition of this chapter in Volume Four of this series,' a tremendous amount of work has been published in the field of pheromone synthesis. Simple but unique structures that can frequently be seen among pheromone molecules became favorite targets of synthetic chemists to test their methodology and strategy in pursuit of simplicity, selectivity, and efficiency. It is therefore very difficult to write a comprehensive review on pheromone synthesis. However, it is the aim of this chapter to summarize almost all of the notable syntheses in the pheromone area published between April 1979 to February 1990. Thus, this chapter will be of service to those chemists who want a quick view of the existing synthetic methods for each of the individual pheromones. The pheromones described in this chapter are classified according to the structural type, as in the first edition. Because the synthesis of optically active pheromones is now a common practice, enantioselective synthesis has been included in each section instead of being made into an independent section, The relationships between absolute configuration and pheromone activity are briefly summarized at the end of this chapter. There are a number of recent monographs and reviews on pheromones. The following brief listing highlights the focus of literature published within the time frame of this chapter. A monograph on all aspects of pheromone research-including isolation, structure determination, synthesis, and estimation of enantiomeric purity-was published in 1984.2 Synthetic methodologies useful in preparing chiral pheromones were thoroughly r e ~ i e w e d . ~

2. GeneralMethods

3

The present status of pheromone biochemistry was compiled as a monograph.4 Three general reviews on insect pheromones become Ritter reviewed steric factors in pheromonal pest control;8 he also reviewed his own applied research on semio~hemicals.~ A concise review on chiral insect pheromones was published in Czech. I' Schneider reviewed the problem of insect olfaction. I' A comprehensive review became available on structure determination of pheromones by combined microchemical and gas chromatographic methods. The following additional reviews were published: a short reviewI3 an account of the background of pheromone research and its application in insect pest c o n t r o ~ 'I5 ~' a thorough review covering the literature published in 1982 and 198316 a review on isoprenoid pheromones (in Russian)I7 a pedagogical review on chirality in insect communication18 an account of the pheromone metabolism in insects"

'*

2. GENERAL METHODS Some useful methods for the synthesis and analysis of pheromones are listed below.

A. Useful Synthetic Methods

( I ) Alkylation of Acetylides in DMSO In addition to the existing procedures for the alkylation of 1-alkynes,' Chong and Wong proposed a method employing methyllithium (base) and DMSO (solvent).*' As shown in Eq. 1, terminal acetylenes afford disubstituted acetylenes in good yield.

(7747% yield) R=CH,OTHP, CH,OCH,Ph, Ph, CH(OEt), R=n-C,H,,, n-C,,H,, Me,CHCH, X-CI. Br. I

4

The Synthesis of Insect Pheromones, 1979-1989

(2) Alkylation of Acetylides in the Presence of DMPU Bengtsson and Liljefors employed DMPU (1,3-dimethyl-2-0xohexahydropyrimidine) as a good substitute for the carcinogenic HMPA in the alkylation of lithium acetylides (Eq. 2).2' 1) n-BuLVTHF

H-CS-(CH,),OTHP

Me(CH,),-C=C-(CH,),OTHP

(91-93%) (DMPU)

(2)

(3) Wittig Reaction in a Heterogeneous Medium The Wittig reaction can be carried out in a solid-liquid medium under mild conditions in good yield as shown in Eq. 3.22Wittig chemistry as used in pheromone synthesis was reviewed by Bestmann and V o s t r ~ w s k y . ~ ~

R'-CHO 0.1 rnol

+

'0uo

Ph3PtCH,R2Bi 0.12 rnol

R'=h(CH,),

(100 ml), $CO,

(15 a)

>

HO , (2 rnl)

(70-73%)

R2=Me(CH,),

Me(CH2),,

'

R1-CH=CH-R2 + Ph,PO E:2=15-20:80-85

n=10-14

(4) Kolbe Synthesis of Unsaturated Pheromones Kolbe electrolysis was used for the coupling of 5-alkynic acids and half esters to give alkynic acids, which could be converted into unsaturated pheromones (Eq. 4).24 R-C=C-(CH,),CO,H

R=Ef n-Pr, n-Bu

+ HO,C(CH,),CO,Me n=2,3,4,6

e' > ~ -2)1) OH'

R-C4-(CH,),+,C02H

(45-59Yo)

(4)

2. General Methods

5

(5) Olefin Inversion

Inversion of the geometry of alkenes is a useful method in pheromone synthes ~ sTreatment . ~ ~ of alkenes with N-chlorosuccinimide in trifluoroacetic acid results in anti-addition of the element of trifluoroacetyl hypochlorite. Heating the vic-chlorohydrin trifluoroacetate with sodium iodide in DMF produced alkenes with inversion of the geometry (Eq. 5).26

(6) Reduction of Diynols to Enynols 2,4-Diyn-l-ols can be reduced to (2E)-en-4-yn- 1-01s by treating the corresponding lithium alcoholates with diisobutylaluminum hydride (Eq. 6).27 1) n-BuU/THF, -8OOC Me(CH2),C~C-C~C-CH,0H

2) (i-Bu)$lH, -80°C

3) H,O

V

H Me(CH,),C=C-C=CCH,OH H

(72%)

(6)

(7) Reduction of Diesters to Diols Aksenov et al. reported that the preparation of a,o-diols from diesters by reduction with lithium aluminum hydride was made possible in toluene by the addition of 5-10% of THF, glyme, or diglyme (Eq. 7).28

EtO,C(CH,),CO,Et

LiAIH,

3

toluene + 5-10% THF, glyme or diglyme

HO(CH,),OOH

(71

6

The Synthesis of Insect Pheromones, 1979-1989

(8) Preparation of w-Bromo-a-alkanolsfrom a, w-Diols

Pure w-bromo-a-alkanols were prepared in good yields by refluxing a mixture of a,w-diols, 48% hydrobromic acid and benzene using a Dean-Stark water separator (Eq. HO(CH,),OH

n =2-12

>

48% HBr/C,H,

reflux (-H,O) (40-90%)

Br(CH,),OH

(9) Preparation of o-Acetoxy-a-alkanols from a, w-Diols Monoacetylation of a,w-diols was achieved in high yield by the use of continuous extraction of the reaction mixture consisting of a,w-diols, acetic acid, water, and sulfuric acid (Eq. 9).30 HO(CH,),OH n=8, 10, 12

AcOH-H20, H2S04

> AcO(CH,),OH

Continuous extraction with hexane, cyclohexane or cyclohexane-CCI, (75-94%)

(9)

(1 0) Preparation of w-t-Butyldimethylsilyloxy-a-alkanols from a, w-Diols McDougal et al. silylated the monosodium alkoxide salt of a,w-diols with one equivalent of t-butyldimethylsilyl chloride to furnish monosilylated material in good yield (Eq. A polymer-supported organosilyl protecting group was also used in pheromone synthesis.32

HO(CH,),OH n=21.10

1) leq NaHRHF 2) t-BuSiMe,CI (77-97%)

>

Me I HO(CH,),OSit-Bu I Me

(11) Mild Protection and Deprotection of Alcohols as t-Butyl Ethers

t-Butyl ether was found to be the most appropriate protection for o-hydroxyalkyl halides when they were to be converted into organolithium or Grignard reagents. w-t-Butoxy organolithium and Grignard reagents can be prepared in ether, exactly like the nonfunctionalized ones, and their reactivity is normal.33

2. General Methods

7

The protection and deprotection of alcohols as t-butyl ethers can be achieved under the mild conditions exemplified in Eq. 11 .34 ROH

+

3-5eq Ac,O > ROAc > Rot-BU hexane, room temp 0.1-0.3eqFeCI,

AmberlystH-15

(11)

E$O,2OoC, 2-15hr

3-10 hr

(12) Solid Phase Synthesis A method different from that developed by Leznoff3’ was devised by Chan and H ~ a n g . ~They ’ prepared polymer-anchored diphenylchlorosilane and used it for the protection of the hydroxy group. Equation 12 illustrates its use in the synthesis of (Z)-g-tetradecenyl acetate (fall armyworm moth pheromone).

copolymer (1% crnss-link) Me(CH,),PPh,B(

Ph

1) (n-Bu),NF/CH,CI,

~io(CHz)8CH-CH(CHz)3Mo2) AczO Ph (43% overall)

Other synthetically useful methods are: (1) vitamin B,,-mediated electrochemical reaction^;^^ (2) carbocupration reactions;37 (3) stereodirected synthesis with a-haloboronic (4) heteroatom-assisted substitution of acyclic secondary tosylates with lithium dialkyl~uprates;~’ and ( 5 ) semi-hydrogenation of acetylenes using homogeneous catalysis with (dba)*Pdz* CHCl, * Ar,P, although the ZIE selectivity was poor.4‘

B. Useful Analytical Methods Reverse-phase TLC and HPLC were shown to be useful for the separation of pheromone^.^' I3C NMR spectroscopy was employed for the assignment of the geometry of carbon-carbon double bond(s) of olefinic Methods were reviewed for determining the enantiomeric purity of pherom o n e ~ . Slessor ~ , ~ ~ et al. described a method for determining the enantiomeric composition of chiral alcohols, lactones, and hydroxy acids in quantities rang-

8

The Synthesis of Insect Pheromones, 1979-1989

ing from 25 ng to 10 pg.46Derivatization of the substance with enantiomerically pure acetyllactyl chloride, followed by GLC analysis enables enantiomeric estimation.

3. ALKANES AS PHEROMONES

A. 2-Methylheptadecane 1 (C1BH38) The title hydrocarbon is the sex pheromone of the tiger moth (Holomelina aurantiaca; Arctiidae species). This achiral alkane was synthesized by Naoshima employing diethyl 3-oxoglutarate as the starting material (Scheme l).47 Another synthesis was reported by Bhalerao (Scheme 2).48

Scheme 1

Me(CH2),,CH=CH,

Me

I > Me(CH,),,CH(CH,),CHCOzMe

1) Hg(0Ac)dAcOH

I

2) CH,=CC02Me

ICI.

OAC

UAIH, ___j (70%)

3) NaBH,

Me 1) PzOa/CsHE.heal M~(CH,),,CH(CH~~,~HCH,OH 2) Raney-NirEtOH AH

> Me(CH2),,CHMeZ 1

Scheme 2

B. (5S,9S)-5,9-Dimethylheptadecane 2 (C 19H40) The mountain-ash bentwing (Leucoptera scitella) is a pest in the apple orchards in Hungary. Its female-produced sex pheromone was identified by Francke et al. as 5,9-dimethylheptadecane (2).49 A synthesis of a diastereomeric mixture of 2 was achieved by the mixed Koble electrolysis of (*)-3-methylheptanoic acid and (+)-4-methyldodecanoic acid (Scheme 3) .49 Helmchen’s synthesis of the four stereoisomers of 2 was followed by their bioassay to reveal (5S,9S)-2, [aID 2.1 (CHCI,) as the natural pheromone.”

+

O

3. Alkanes as Pheromones

.sv\Nv AZH ' HOzC

Me3N/MeOH Pl.elecvod0 0.3Alcrn2,2hr

9

'

(305h)

VdVdNw

(SS.SS).Z

2

Scheme 3

Other stereoisomers neither synergize nor inhibit catches with (5S,9S)-2, and, therefore, a diastereomeric mixture is practically u ~ e f u l .Another ~ ~ . ~ multigram ~ synthesis of a diastereomeric mixture of 2 was reported by Rama and Capuzzi (Scheme 4).5'

Scheme 4

C. 3,7-Dimethylnonadecane 3 (C, IH44) The female-produced sex pheromone of the alfalfa blotch leafminer (Agromyza frontella) was identified as 3,7-dimethylnonadecane (3).52 A diastereomeric mixture of 3 was synthesized, as shown in Scheme 5, and shown to be bioactive.

''

Me(CH,), P'P h,Bi

*

Me(CH,),,CH=&(CH,),I

1) ll-&UE$O

a

2) MeC(CH,),CI

PhP W C

Me

Me

E~=CH(CH,),C=CH(CH,),,Me I

>

a

Me

Nal

CI(CH~)~~-CH(CH~),~M~

Me

Me(CH2),,CH=C(CH,),P'Ph3l' I

* Hpd-C

Scheme 5

1) wBuliTTHF

2)MeSEI 0

Me Me I E~~H(cH,),cH(cH,),,M~

3

10

The Synthesis of Insect Pheromones, 1979-1989

D. 15-Methyltritriacontane4 (C34H70) This is the female-produced sex-stimulant pheromone of the stable fly (Sromoxys culcitruns). A synthesis of ( f ) - 4 is shown in Scheme 6.53

Two syntheses were reported for the enantiomers of 4. Scheme 7 shows the synthesis reported by Sonnet.54The chiral part of the molecule was synthesized via optical resolution. The enantiomeric bromides were then converted to the cuprates and coupled with tridecyl iodide to give the enantiomers of 4. Their bioassay results are not yet published. Naoshima and Mukaidani synthesized the pure enantiomers of 4 in good overall yield, starting from (I?)-( +)-citronellic acid (Scheme 8 v 3

E. 15,19-Dimethyltritriacontane5 (C35H72) This alkane is also the mating-stimulant pheromone isolated from female stable flies (Stornoxys culcitruns). Sonnet prepared (15R,19R)-,(15S,19s)-,and meso-5 (Scheme 9).54The starting chiral alcohol was obtained by resolution in the same manner as shown in Scheme 7.

3. Alkanes as Pheromones

Me(CH,),CH-PPh, (92%)

(Iss,les).5

Scheme 9

11

I2

The Synthesis of Insect Pheromones, 1979-1989

F. rneso-15,23-Dimethylpentatriacontane 6 (C37H76) The title compound is the sex-stimulant pheromone of the female tsetse fly (Glossina palfidipes).A simple synthesis of a diastereomeric mixture of 6 was reported by Carlson et al. (Scheme lo)? Both the enantiomers of 6 , as well as

Scheme 10

meso-6, were synthesized from (I?)-( +)-citronelk acid, employing the alkylation of the dianion derived from methyl acetoacetate as the key-step (Scheme 1 l).56 Only meso-6 was shown to be b i ~ a c t i v e . ~ ~

(13R,23R)-B (13S.23S)B (25% overall yield) (37% overall yield) mp 45-46.5OC mp M.s-~E~'c [a],,= -0 26' (CHCi,) [a],," +0.25°(CHC13)

mesod (59% l r m (R)-Bl mp 34-34.5'~

Scheme 11

3. Alkanes as Pheromones

G. meso-17,21-Dimethylheptatriacontane 7

13

(C39H80)

This is the female-produced sex-stimulant pheromone of the tsetse fly (Glossina morsitans morsitans). All of the three possible stereoisomers were synthesized by Helmchen (Scheme 12).5s The enantiomers of A were synthesized either by Me(CH,),,AC02H

+ HzN\rOH Ph

(1 7R.21 R)-7, (17S,215)-7 and meso-7

meso-7

Scheme 12

optical resolution or by asymmetric alkylation. By combining the enantiomers of A, (17R,21R)-, (17S,21S)-, and meso-7 were prepared. Only the meso-isomer was shown to be b i o a ~ t i v e . ~ ~

H. 15,19,23-Trimethylheptatriacontane8 (C40H82) The title compound is also the sex-stimulant pheromone isolated from the female tsetse fly (Glossina morsitans morsitans). Two new syntheses of its dias-

14

The Synthesis of Insect Pheromones, 1979-1989

tereomeric mixture were In the earlier synthesis, geranyllinalool (A) was converted to a symmetrical intermediate B, the chain elongation of which by a Wittig reaction completed the construction of the carbon skeleton (Scheme 13).60 Naoshima et al. utilized diethyl 3-oxoglutarate as their symmetrical building block to obtain a diastereomeric mixture of 8 (Scheme 14).6’

8

Scheme 13

0 WCH,),,

&OMS

loluene

1

(CH2)13Me

NaOH aq

(33%)

4. Pheromone Hydrncarbon with a Terminal Double Bond

15

4, PHEROMONE HYDROCARBON WITH A TERMINAL DOUBLE BOND

A. (S)-14-Methyl-l-octadecene 9 (CI9H3*) The title compound 9 was isolated and identified as the sex pheromone of the peach miner moth (Lyonetia clerkella), which is one of the destructive pests in the peach orchards of Japan. The first synthesis of (*)-9 was executed at the time of its isolation for the purpose of identification.62 That synthesis is lengthy and inefficient (Scheme 15).62Two more efficient syntheses of (k)-9were pub-

-

HO(CH,),,OH

> -HBr

HO(CH,)12Br

Ph P

A>HO(CH,)l,P’Ph,Br~

1) base

1) NH , *,

H20,

2) Me(CH,),COMe

2) CrO,*C,H,N’

Scheme 15

lished later by chemists in industry. Manabe et al. introduced the double bond of (*)-9 at the final stage of their synthesis (Scheme 16),63 while Yamamoto

dgBr +

48%HBr (89%)

Br(CH,),,OTHP

1) Li,CuCI,/THF

2) TsOH/aq MeOH (77%) Br

t-BuOK DMSO (55%)

>

(k)-9

Scheme 16

and Fukumoto used ally1 chloride as one of their starting materials (Scheme 17).64 Four different syntheses of optically active 9 were reported. In Mori’s first synthesis, the enantiomers of methyl 0-hydroxyisobutyrate (A) were employed as the chiral building blocks (Scheme 18).65 A is of microbial origin and com-

The Synthesis of Insect Pheromones, 1979-1989

16

Scheme 17

A

TsCl (98%)

2) TSOHN~OH (72%)

3) TsCl

1) m

g Li,CuCI,TTHF

B

r

>

2) SiO,-AgNO, chromatog. (9-14%)

(S)-9

[alO2' +1 .21° (n-hexane)

(R)-9

[a],*'-1.06' (n-hexane) Scheme 18

mercially available. In the final step of the synthesis, however, the yield was quite modest due to the difficulty in separating 9 from other hydrocarbons generated as byproducts. (R)-( +)-Citronellic acid was used as the starting material in the second synthesis of (R)-9 and (S)-9 (Scheme 19).66Only (S)-9 exhibited the pheromone activity, although (f)-9 was also active.67 The third synthesis by Sonnet et al. was based on the optical resolution of an intermediate (Scheme 20).68 Serebryakov converted (S)-( +)-3,7-dimethyl-l,6-octadiene into (S)-9 (Scheme 21).69

4. Pheromone Hydrocarbon with a Terminal Double Bond

1) Me,CuLl

1) TsCl

2) NaOH (76%)

(W-9

(70%)

[a]:' -1.24' (n-haxane)

(65%)

(75%)

Scheme 19

1) LDA EtCO,H

2) Me(CH2),B? (94%)

,&

1)LDA. 2) wnc HCI

3)UAIH, (88%)

'

&H

1) SOCI, 2) H,NCH(Me)Ph

Tco2H 3) Recryslallizallo"'

4

N

h

\

P

h

(40%)

1) Ph,PBr, 2) Nal, Ph,P

>w

i

P ' P h , l '

Scheme 20

1) n-BuU

>

2) OHC(CH2),,OTHP (67%)

17

18

The Synthesis of Insect Pheromones, 1979-1989

1) 5G% AcOH

2)HIO. 3j N ~ H ,

(eo%)

1) TsCl 2) MeMgI, LI,CUCI,~THF (78%)

> (59-9

[a]Op 4.6' (CHC13)

Scheme 21

5. PHEROMONE ALCOHOLS AND ACETATES WITH AN E-DOUBLE BOND

A. (E)B-Nonen-1-01 10 (C9HI80)and (E)d-Nonenyl Acetate 11 (C I I H2002) Males of the Medit'erranean fruit fly (Cerariris capitafa) produce (E)-6-nonen1-01 10 as the sex pheromone. The corresponding acetate 11 is the attractant for the female melon fly (Dacus cucurbitae). A Wittig-Homer reaction was employed to furnish 10 (Scheme 22).70*7'

\J' 0

(81%)

NaH

DMF (98%)

'

,H

c, = c, ti

Scheme 22

10

(CH2150H

5. Pheromone Alcohols and Acetates with an E-Double Bond

19

A synthesis of 10 was also achieved by the palladium-catalyzed reaction of (El-1-chloro-1-butene with a Grignard reagent (Scheme 23).72

+

CiMg(CHz),OMP

1) (Ph,P),Pd/C,H,-THF 2) Amberlife IR 120 (60%)

lo

--

Scheme 23

Vinylic organoboranes were shown to be useful in the synthesis of (E)-al(E)-6-Nonenyl acetate 11 was synthesized via thexylchloroboranedimethyl sulfide (Scheme 24) .75 This procedure affords the (E)-pheromones of >97 % chemical purity essentially in a one-pot synthesis.

11 (74% overall yield)

Scheme 24

Another one-pot synthetic method for @)-pheromones utilizes monohydroThe reboration of 1-alkynes with borinane as the first step (Scheme 25).73*75

0

+

EtCsCi

-78OQ'C

H

AcOH ___)

NOH-THF 8O0C

O p

> - THF

H'

c=c\

O°C-room temp

(CH

/OMe

'" 'OMe

HzOz NaOH

Scheme 25

>

II

C=C\

(CH,),OH

H' 10 ..

(80% overall yield)

20

The Synthesis of Insect Pheromones, 1979-1989

sulting B-(E)-1-alkenylborinanes, when treated with sodium methoxide, furnish intermediates containing the seven-membered borepane moiety, which yield (E)-pheromones upon protonolysis and oxidation. The products are of r 99% chemical purity. A synthesis of 11 was executed by the deoxygenation of the corresponding epoxide with diphosphoms t e t r a i ~ d i d e .The ~ ~ pure epoxide was obtained by chromatographic (SO2) purification of the mixture of epoxide isomers.

B. (E)-7-Dodecenyl Acetate 12 (C,4H2602) This is the sex pheromone of the false codling moth (Cryprophleviu leucotretu). Three different syntheses of 12, by means of transition metal catalysis, were reported r e ~ e n t l y . ~ * - * ~ In Sato's synthesis (Scheme 26), hydromagnesiation of A with isobutylmag-

Me,SiC=C(CH,)60H A

__[ ," 2eq Me2CHCH2MgBr

c = c/(CH2),0H

\ /

Me(CH2)3

\

H

Cp,Ti Cl2

1 ) Iz/H20

2) Ac20/C,H,N (84%)

(CH2)60H

=,C

Me(CH,),

]

Me(CH2),1 CulKHF (84%)

/H

c, = C\ H (CH2),0Ac 12 (E:Z=96:4)

Scheme 26

nesium bromide in the presence of titanocene dichloride was followed by treatment of the resulting Grignard reagent with alkyl iodide to yield a vinylsilane, which was desilylated and acetylated to give lX7* Naso and his co-workers developed a general method for the synthesis of (E)-pheromones employing a nickel catalyst (Scheme 27) ,79 Starting from ( E ) l-bromo-2-phenylthioethene,two cross-coupling reactions of the Grignard reagents in the presence of a nickel catalyst yielded 12 of high chemical purity. Many (E)-pheromones were synthesized by this method. Rossi and Carpita prepared 12 by the cross-coupling of an alkenyl bromide with a Grignard reagent in the presence of dichloro [ l , l ' bis(diphenylphosphino)ferrocene]palladium [ = PdCl,(dppf)] .80 The reactivity of A (Scheme 2 8 ) was higher than B in this coupling reaction. A mixture of A

5. Pheromone Alcohols and Acetates with an E-Double Bond

/H

-

PhS\

THPO(CH,),MgBrflHF-Et,O

c = c,

H’

Br

PhS,

H ’

C ’ H

NiCI,(Ph,PCH,CH,PPh,)

21

= c, (CH,),OTHP

(86%)

Me(CH&3,

1) M(CH213MgBr

H ,

= ’\(

NiCI,( Ph,PCH,CH,PPh,)

CH,),OAc

2) Ac,O

(81%)

Scheme 27

c;cf

n

H‘

PdCl,(dppf) -n THF (79.5%)

A

(+

m

Br

Me(CH,),, C ’ H

M(CH2)3,

/C =)c‘:

H

B

n CH,=CH(CH,),MgBr

H

C

1) 9-BBNTTHF

/H

= c,

+

2) OH-, H202

(CH,),CH=CH,

>

3) AcCI/C5H5N

H

(75%)

D

(CH,),OAc

12 (E=98%)

Scheme 28

+

and B (molar ratio = n : m) therefore reacted with n/(m n) eq of C to give only the desired product D (Scheme 28). This pheromone 12 was also synthesized by other methods, which have already been ~umrnarized.’~~’~ Quite a lengthy and classical synthesis of 12 by Vig et al. (Scheme 29)81 contrasts the brevity of the aforementioned syntheses of 12 by modem methods.

C. (El-8-Dodecenyl Acetate 13 (C14H2602) This is the minor component of the pheromone of the oriental fruit moth (Grapholitu molestu). A synthesis of 13 employing classical acetylenic chemistry was reported by Mithran and Mandapur.82 A more interesting synthesis by Schlosser et al. utilized (,??)-selective variant of the Wittig reaction (Scheme 30).83This betaine-

22

The Synthesis of Insect Pheromones, 1979-1989 MsCVESN

(50%)

(94%)

E o Z C W O T H F

MeOH NaOH

>

HMPA l800C'

E Q C w o T H p "08

room temp

Et0,C

(90%)

(60%)

E o 2 C w o T H p

3 (so%)

PMgBr THF

OHCmoTHp

PCC, NaOAc Ho-oTHP (70%)

OH

>

P O -

OTHP

(70%)

@O

heat OTHP

1

(50%)

>

OHC-

~

LiAIH,

0

(80%)

OTHP

HO

'

NaCH(CO,Et), C,H,-DMF

Mso-oTHP

CH,CI,

MsCl

OTHP

~

EGO

(90%)

Me,CULi MsO

OTHP-

CH,CI,

EGO

(60%)

1) TsOHlMeOH

oTHP

OAc

2) Ac,o,c,H,? i (56%)

12

Scheme 29

2 Phti-tiBr

[Ph,P'-CH,(CH,),OHjBr*

Ph,6-$H(CH2),0Li

___j

THF-E$O

1) Me(CH,),CHO 2) PhLbLiBr

iiBr

CHoU Ph,P'-k-(CH,),OLi iiBr

I ) HCI-EGO

> -

2) 1-BuOK (74%)

Me(CH,),

p= c,

H

c=c,

_j

(CH2)7OH

E:Z=99:1

Scheme 30

H' 13

(CH,),OAc

5. Pheromone Alcohols and Acetates with an E-Double Bond

23

ylide modification of the Wittig reaction allows the synthesis of (E)-alkenes with an isomeric purity of 99% ~

D. (E)-g-Dodecenyl Acetate 14 (C,4H2602) This is the pheromone component of the red bollworm moth (Diparopsis castanea) and the cereal tortrix moth (Cnephasia purnicana). The European pine shoot moth (Rhyacionia buoliana) also uses 14 as its pheromone. Bestmann et al. synthesized 14 as shown in Scheme 31.84 H MeC=CCH,Br H

(W3P

>

OP(OEt), H I MeC=CCH(CH,),OTHP

H

H EtC=C(CH,),OH H

0

H II MeC=CCH,P(OEt), H

LIAIH,

> -

EbO

2) Br(CH,),OTHP

H EtC=C(CH,),OTHP H

,

Ac,O/C,H,N

1) n-BuLi

____a

TsOH

aq MeOH

(33% overall)

Et\

(72%)

>-

H

/

c=c

\

HI

(CH,),OAc

14

Scheme 31

E. (E)3-Tridecenyl Acetate 15 (C15H2802) The female-produced sex pheromone of the tobacco stem borer (Scrobipalpa heliopa) was shown to be (E)-3-tridecenyl acetate 15. It was synthesized by means of classical acetylenic chemistry (Scheme 32).85

Me(CH,),Br

+

1) Na/NH3

2) TsOHlMeOH

LiNH,

> -

HC=C(CH,),OTHP

Me(CH,),CrC(CH,),OTHP

NHflHF

H Me(CH2),C=fi(CH,),0H

Ac,O C5H5N

Me(CH,),\

/H

c=c H’

\(cH,),oA~ 15

Scheme 32

The Synthesis of Insect Pheromones, 1979-1989

24

F. (E)-11-Tetradecenyl Acetate 16 (C16H3002) This, together with its (Z)-isomer, is the sex pheromone of oak leafroller moth (Archips semiferunus) and the omniferous leafroller moth (Plutynotu stulrunu), Chan and Koumaglo synthesized a mixture of 16 and its (2)-isomer in a 78 :22 ratio, corresponding to that found in the case of the natural pheromone.86 Their “tunable stereoselective alkene synthesis” is based on the variation of the stereoselectivity of iododesilylation of terminal (E)-vinylsilanes with a changing amount of Lewis acid (Scheme 33).86 Me,Si t

/H

c, = c,

H

H

I, AICI, (l.leq)

/

CH2CI20 Doc

\

_____a ICH=C

(CH,),,OAc

(CH,)

1,OAc

16 (E:Z=78:22)

Scheme 33

A conventional acetylenic route was also employed to prepare 16 and its (Z)-isomer, involving the Birch reduction and ~emi-hydrogenation.~~ Other methods, already discussed, were also employed for the synthesis of 16.72.75*88 G. (E)-12-Tetradecenyl Acetate 17 (C16H3002) In combination with its (Z)-isomer, 17 is the pheromone of the Asian corn borer moth (Osrrinu firnuculis). Kang et al. synthesized 17 starting from 12-tetradecyn-1-01 THP ether by the Birch reduction of the triple bond, while its semihydrogenation gave the (Z)-isomer of 17.” Chan and Koumaglo prepared a 1 : 1 mixture of 17 and its (Z)-isomer (Scheme 34).86 H

1’, SnCI, (0.4eq)

/

(CH,),,OAC MeMgBr

> -.

Li,CuCI,TTHF

CH2CIaOoC

,H

-\

c=c H’

’(cH,),,oH

’

Ac,O

& C5H5N

Scheme 34

=

H

/

ICH C,

(CH,),,OAc

Me,

c=c‘

H‘

17

’(CH,),,OAc

6. Pheromone Hydrocarbons and Acetates with a Z-Double Bond

25

H. (El-11-Hexadecenyl Acetate 18 (C18H3402) This is the pheromone component of the sweet potato leaf folder moth (Brachmia macroscopa) and some other species such as the cabbage moth (Mamestra brassicae) and Sceliodes cordalis. Sonderquist and Anderson reported a highly stereoselective synthesis of 18 by their acylsilane-ylide chemistry (Scheme 35).90 0 II Me(CH,),CSiMe,

+

Ph,P=CH(CH,),CH=CH,

Lil

Me(CH2)3\

THF

Me,Si

(48%)

,H

c, = C\

(CH2),CH=CH

Scheme 35

6. PHEROMONE HYDROCARBONS AND ACETATES WITH A 2-DOUBLE BOND A. Muscalure, (23-9-Tricosene 19 ((&H4,) This is the female-produced sex pheromone of the house fly (Musca domestica). Many new syntheses of 19 have been published based on carbanion chemistry, organotransition metal chemistry, organoborane chemistry, etc. Naoshima et al. synthesized 19 by alkylating diethyl 3-oxoglutarate with oleyl bromide and ethyl iodide (Scheme 36).9'

Scheme 36

26

The Synthesis of Insect Pheromones, 1979-1989

Yadav et al. dialkylated tosylmethyl isocyanide, and the product was reduced with lithium in liquid ammonia to give 19 (Scheme 37).92*93

%;,

LiNHdNH,

m(CH,),Br (75%)

> Me(CH,)7C=C(CH2)30H

1) HdPd-CaCOflexane 2) MsCVEt,N Me(CH,)7,

>

3) Nal/Me,CO

/(CH2)31

/C H

= C\

H

A

(80%)

Scheme 37

Me(CH,),CHO

+

A Me(CH,),CH=CH,

H H Me(CH,),C=CCH20Ac

-

+-

Ph3PCH(CH,),,Me ’instant ylide’

H\

(8ro/.)

..,-K’......

n-BuLi

> -

Me(CH2), (CH2),,Me 19 (2:E=97.5:2.5) 1) FB(OMe),

6..

Me(CH,),CH-CH-CH,

I-BuOK

2) 40, 3)Ac,O

H \ /C

Cul

Me(CH,), Scheme 38

/H

c, = C\

= c,

I

19

H (CH2)44e

The first Scheme 38 illustrates the synthesis of 19 by Schlosser’s approach is the use of “instant ylide,” which is a mixture of sodium amide and the phosphonium salt. By the addition of ether or THF, ylide can be generated instantly. Reaction of ylide A with nonanal furnished 19 in 81 % yield with E : Z ratio of 2.5 : 97.5. Their second approach was the coupling of dodecylmagnesium bromide with (Z)-2-undecyl acetate to give 19 of ca. 97.5% Fiandanese’s synthesis of (E)-alkenes (Scheme 27) could be modified to give ( Z ) - a l k e n e ~Muscalure .~~ 19 of 2 98.3% chemical purity was obtained as shown in Scheme 3ge7’

6. Pheromone Hydrocarbons and Acetates with a 2-Double Bond

H,

/H

Phd

H\

Me(CH,),,MgBr

c=c

\Br

/C= c,

PdCt2(PPh3)2>

Me(CH,),MgBr

>

NiCI,(Ph,PCH,CH,PPh,) (75%)

H

/

PhS H

(CH,),Me

H

\

WCH2)7

27

/

c = c\

/

(CHJ12Me

19

Scheme 39

Organoborane chemistry was extensively used for the synthesis of 19. In Brown’s first synthesis of 19, base-induced iodination of a vinylborane A provided 19 (Scheme 40).95-96 The second synthesis of 19 by Brown et al. utilized Me(CH,),,CH=CH, LiAIH,

-> ,

+ BHBr,.SMe,

Me(CH2)7C~CHMe(CH2)12B-Br \

EGO

EGO 12

NaoMe (59%)

/

/

\

19

H’

\(CH,),Me

A

H

H\

c=c

Me(CH,),

/

c=c

Me(CH,),,BHBr.SMe,

+

Me(CH,),,CH2CH,BBr2~SMe,

(CH,),Me Scheme 40

their improved procedures for the protonolysis of alkenyldialkylboranes to give (2)-alkenes of high purity.97 Thus, muscalure 19 was synthesized by hydroboration-protonolysis of 9-tridecyne, which was prepared by iodination of lithium (1-decyny1)tri-tridecylborate (Scheme 41).98 Me(CH2),,CH=CH2

BH3 + We(CH2),,13B THF

Me(CH,),C=CLi THF

-78’C 9-BBN

H\ Me(CH,),, overall) Scheme 41

/H

/C= C\

(CH,),Me 19 (%Yo pure)

The Synthesis of Insect Pheromones, 1979-1989

28

Chan's organosilicon approach for the synthesis of 19 is shown in Scheme 42.99 1) n-BuLi. 1-BuOK 85 : 15

3) HI

H H Me(CH2), ,C=C I

ICI, KF

> -

(87%)

Me(CH,),ZnCI

H\

/H

/c = c,

(Ph,P),Pd (96%)

Me(CH,It2

(CH,),Me

19 (Z:E=96:4)

Scheme 42

One of the (Z)-double bonds of 1,5-~yclooctadieneA (Scheme 43) served as the (Z)-double bond of 19.'O0Conversion of an Indian natural product, aleuritic acid B, to 19 was also reported.'0'''02

+, 5

H HO(CH,),

OH

3 Me(CH,),,

(CH2)7C02H HO H Aleurilic acid B

HHc~~CH2),2Me It

5

H

OH

HO

(CH2)7C02H H

Scheme 43

Another synthesis of 19 is based on the connection of the alkenyl and alkyl chains by using acetone N,N-dimethylhydrazone as the connective synthon (Scheme 44). '03 B. (Z)-S-Decenyl Acetate 20 (CI2H,,O2) This is the pheromone component of the turnip moth (Agrotis segetum), and was synthesized from 1-hexyne and 4-bromo-1-butanol THP ether. The resulting alkynyl THP ether was hydrogenated over Lindlar catalyst to give (2)-5-

6. Pheromone Hydrocarbons and Acetates with a 2-Double Bond

1) LiNHdNH,

>-

HdLindlar-Pd

Me(C!i2),CzC(CH2),0H

29

>

2) Me(CH,),Br

"Me, Me(CH2)7,

1) n-BuLilTHF 2) Me(CH Br

II

/(CH,),CMe

>

2)e

c=c

H'

k

NaBH, Me(CH ) MeOH (95%)

-

3) dil HCI/Et,O (80% from A)

OH

+

0

27\

I

'(CH2)4CH(CH2)7Me c=c \

H'

H

II

/(CH2),C(CH,),Me

c=c

\

H'

H

1) MSCl

l(CH2),2Me

2) LiAIH4

Scheme 44

H'

c = c\

H

19

(96%)

decen-1-01 THP ether. It was then converted to 20 by acetyl chloride in acetic acid. '04 Liljefors et al. published structure-activity studies on 20 and related compounds using molecular mechanics. Io5* '06

C. (2)-7-Dodecenyl Acetate 21 (C14H2602) The cabbage looper (Trichuplusia ni) uses this acetate 21 as its pheromone. Bestmann et al. synthesized 21 by the Wittig reaction employing the ylide prepared by treating a phosphonium salt with sodium hexamethyldisilazide (Scheme 45).'07 Horiike and Hirano also synthesized 21 by a Wittig route employing

-

H H Me(CH2),C=C(CH2),0Ac 20

Me(CH,),CH=PPh,

OEt

H

\

H

c=c\ /

Me(CH&3

O3

2)Ph,P

1) LiAIH,

(CH2)&02Et

2) Ac2O/C5H,N

Scheme 45

>

OHC(CH,),CO,Et

The Synthesis of Insect Pheromones, 1979-1989

30

[Ph,G(CH2),0H]Bi

+Ylide NaH/DMSO

1) Me(CH,),CHO

THF, O°C

2) Ac20 (53-76%)

-

Me(CH,),

H\ /C

H

/

= C\ 21

(CH,)6OAc

(Z:E=92-94:6-8)

Scheme 46

sodium hydride and DMSO as the base (Scheme 46).Io8 Fiandanese's synthetic method for (E)-alkenes (cf. Scheme 27) was modified to give 1) 0.25eq LiAIH4

CI

H'

+

H \ /C

H

= C\/

h(CH2)3

(CH,),OH

&97%

+

c = C\

2) Me(CH2)3C=CH

(CH,),Me H \ /C

/

(MeO),B(CH,),

(CH,),W

p= c,

AcCl

C5H5.N (92%)

H

=c\

H\

H202, NaOH ____j (78% overall)

H

I

Me(CH,),

(CH2),0Ac 21

Scheme 47

Organoborane chemistry was useful in preparing 21 (Scheme 47).76s'09 Another synthesis of 21 was achieved via lithium (1-alkyny1)borate (cf. Scheme 41).98

Aleuritic acid, an easily accessible (in India) component of shellac, was employed as the starting material for the synthesis of 21 (Scheme 48). The pres-

-

"'

NalO,

HO(CH,),CH(OH)CH(OH)(CH,),CO,H

1) Me(CH,),CH=PPh,

2) Ac20/C5H5N (49%)

>

aq EtOH (81%)

aleuritic acid

H\

k(CH2)3 21 Scheme 48

H

/

c, = C\

(CH,)&AC

OHC(CH,),OH

6. Pheromone Hydrocarbons and Acetates with a 2-Double Bond

31

ence of all parts of the acetate group was found to be very important for the expression of the pheromone activity of 21."'

D. (Z)-8-Dodecenyl Acetate 22 (C 14H2602) This is the sex pheromone of the oriental fruit moth (Grupholitha molesru). SkattebBl employed 1,5,9-~yclododecatrieneas the starting material for the synthesis of 22 (Scheme 49)."*

crystalline

Pb(OAc),

-

> -CHO

C6H6-MeOH

C0,Me

Scheme 49

Julia and Stacino synthesized 22 as shown in Scheme 50.'13The notable step in this synthesis is the stereoselective hydrogenolysis of the sulfonyl group of

A.

Me(CH,),CHO

+

?

PhS(CH,),OH n II U

'

1) 2eq n-BuLiTTHF -~O...-~OC

2) Ac20

Scheme 50

AcO S0,Ph I

I

Me(CH,),CH CH(C H,),OAc

NaOH

> -

dioxane

32

The Synthesis of Insect Pheromones, 1979-1989

Kang et al. employed the Wittig chemistry as shown in Scheme 5 1 to prepare a 92-93 : 7-8 mixture of 22 and its (.!?)-isomer. ' I 4 The mixture with this ratio was found to be quite attractive against the oriental fruit moth. HO(CH,),OH

1) PCC (55%)

> OHC(CH,),OAc

1) 48%HBr/C6H6(78%)

Me(CH,),P+Ph,Brn-BuLi/C,H,

/H

Br(CH,),OAc

H\

+ Me(CH,),

(CH2),0Ac

NaHCO,

(63%)

I(CH2)70Ac

c=c

I

\

H

(7-8%)

22 (92-93%) Scheme 51

E. (Z)-9-Dodecenyl Acetate 23 (C 14H2,502) The pheromone of the European grape beny moth (Eupoecilia (Clysia) ambiguellu) is (Z)-9-dodecenyl acetate 23 of high purity, and even 1 % of its (E)-isomer has an almost total inhibiting effect on its bioactivity. Normant and co-workers prepared pure 23 employing organocopper chemistry as shown in Scheme 52. ' I 5

Et,CuLi

+

2HCaCH Et

1) I(CH,),OAdTHF-HMPA, P(OEt),

2) H30+

H

\

Et'

H

/

c = c,

(CH,),OAc

23 (99.9%2)

(81%)

Scheme 52

6. Pheromone Hydrocarbons and Acetates with a Z-Double Bond

33

The female-produced sex pheromone of the grape berry moth (Paralobesia viteana) is also 23. Julia synthesized 23 by his sulfone method (cf. Scheme 50). I l 3 Reductive decyanation of alkyl nitriles with potassium on alumina (Scheme 53) was the key-step of Savoia's synthesis of 23.Il6 Michelot's syn1) NaCN

>-,

Br(CH,),OH

-

2) DHP, Amberlyst H-15

K-AI,O,

H,

hexam (80%)

Et

p=c\

d

? CN I F=c, ,CH( CH,),OTHP Et (CH,), H\

LDA

NC(CH,),OTHP

EtC=C(CH,),I H H

AcCl

-

"\

(CH,),OTHP

(CH2)80Ac (85%)

23

Scheme 53

thesis of 23 employed tetrakis(tripheny1phosphine) palladium as the catalyst for the cross-coupling (Scheme 54). 'I7

HC=C(CH,),OTHP

"'

H P "

u>

HN=NH

IC=C(CH,),OTHP

C6H6

(87%)

H\

H

/

/C=C,

I

(CH,),OTHP

l)(Ph3P)4Pd/C6H6 2) EIMgWE50

,

3, TsoH/aq MeOH 4) Ac,O/C,H,N (47%)

H\

H

/

c=c

~ t '

23

\

(CH,),OAc

Scheme 54

F. (2)d-Tetradecenyl Acetate 24 (C16H3002) The heart and dart moth (Scoria exclamationis) employs a 95 : 5 mixture of (Z)5-tetradecenyl acetate 24 and (Z)-9-tetradecenyl acetate 26 as its pheromone. Bestmann et al. synthesized 24 by a Wittig route (Scheme 55).'18 The New

The Synthesis of Insect Pheromones, 1979-1989

34

L(CH,),CH-CH,

1) Ph,P 2) NaN(SiMe,),

> P~P-CH(CH,),CH=CH,

Me(CH,),CHO

11 9.BBN

(76% overall)

24

Scheme 55

Zealand leafroller moth (Planotortrix excessana) also uses a mixture of 24 and (2)-7-tetradecenyl acetate 25 as the pheromone. Interestingly, the ratio of 24 to 25 was found to vary continuously from 3 :97 to 7 1 : 29 in individual female moths in New Zealand."'

G. (Z)-7-Tetradecenyl Acetate 25 (C I 6H3002) This is the pheromone of the spotted cutworm moth (Amathes c-nigrum). A full paper of its synthesis appeared (cf. Scheme 38, Ref. 1).Io7 A synthesis of (2)-7-tetradecen-l-o1 by means of organoborane chemistry via B-methylborepane A was reported by Brown et al. (Scheme 56).'*' The

*,c = d M~cIH (,),

\(CH,)~OAC 25

Scheme 56

procedure used for the synthesis of (Z)-7-dodecenyl acetate 21 was also applied to prepare 25 (cf. Scheme 45).Io9In another borane-mediated synthesis of 25, Brown employed borepane A as the starting material (Scheme 57).76The method

6. Pheromone Hydrocarbons and Acetates with a Z-Double Bond

(80% overall)

2:E - 9 9

35

25

11

Scheme 57

used for the synthesis of (Z)-9-tricosene 19 (cf. Scheme 41) was also used for the synthesis of Schlosser’s “instant ylide” was used to prepare 25 (Scheme 5 8 ) . ’ * ’ Subramanian and Sharma converted aleuritic acid to 25 (Scheme 59).’**

Waxy ‘instant ylide’ reagenl

Ac,O

H,

OH

H O ( C H , ) ~ C ~C(CH,),CO,H H d H’

2) Pb(OAc), C,H5N , heal , C“(OAc),’

Aleuritic acid

( 69.h )

pH - C(CH,),CO,H

Ht HO(CH,),C

Hd H’

Me(CH,),’

c:cl

1) HC(OEl), heal

‘(CH2),C0,Ks

-

A d H’

, PhC0,H

2) MeOH , H2S0,

>

( 92% )

1) LiAIH, / THF

H\

H OAc t? AcO(CH,),C C(CH,),CH=CH,

1) Ac,O / CH ,N ,

2) Ac,O/

C5H,N

( 77% )

>

H\

c:c,

HO(CH2)i

(CH,),CO,Me

F

H\

WCH,),‘

c=c

‘(cH,),oA~ 25

Scheme 59

F

1 ) KMO, , adwen-464 C,H,-H,O 2) NaOH , heal

3) H30’ ( 86% )

1) TsCl / C,H,N

2) Nal , Zn / glyme

(74%)

>

The Synthesis of Insect Pheromones, 1979-1989

36

H. (Z)3-Tetradecenyl Acetate 26 (C16H3002) This is the pheromone of the fall armyworm (Spodoptera frugiperda), the smaller tea tortrix (Adoxophyesfasciara),and some other insects such as the summerfruit tortrix moth (Adoxophyes orana) and the heart and dart moth (Scotia exclamationis). Several syntheses of 26 were reported such as Bestmann’s Wittig route,”’ Julia’s sulfone route,’I3 and Michelot’s palladium-catalyzed coupling route.’” An acetylenic route was also recorded by Kang.l14 Mitra and Reddy prepared 26 starting from acetone dimethylhydrazone (Scheme 60). 123 2 eq n-BuU/ THF-HMPA

Me(CH,),Br

HC=C(CH,),OH .. ( 6Ph )

’

Me(CH,),C EC(CH,),OH

H, I Pd.CaC0,

hexane ( 95% )

SO, / THF-Hp ( 73% )

H\

,H

1) aq HCI

\(CH,),OTHP

‘)

c=c

Me(CH,),’

(22%)

H\

Ac20/C5H5N ( 74% )

>

,H

c=c

M S ( C H ~ ) ~ / \(cH,),oA~ 26

Scheme 60

I. (Z)-10-Tetradecenyl Acetate 27 (C16H3002) The sex pheromone of the apple leafminer moth (Phyllonorycrer ringoniella) was suggested to be a mixture of 27 and (4E, 102)-4,lO-tetradecadienyl acetate. 124 Horiike et al. prepared 27 and related (Z)-alkenyl acetates by the Wittig reaction (Scheme 61). 1 2 5 Br

(Ph,P*(CH,),,OH]

1) NsH / DMSO 2) Me(CH,),CHO ( 63% )

H

H

‘c = c/

Me(CH,),’

\(CH,)90A~ 27

Scheme 61

H

Me(CH2)2/ (

H

c=cI

\

\(CH2),0H

z 95% )

Ao,O C,H,N ( 90-95% )

7. Pheromone Alcohols and Acetates with Conjugated Dime and Enyne Systems

37

J. (22-11-Tetradecenyl Acetate 28 (C 16H3002) This is the pheromone component of the oak leafroller moth (Archips semiferanus). This was synthesized by the palladium-catalyzed Grignard-coupling reaction according to Linstrumelle (cf. Scheme 23).72A synthesis via acetylenic route was also reported. I l 4

K. (Z)-11-Hexadecenyl Acetate 29 (C18H3402) This is the pheromone of the purple stem borer (Sesamiu inferens), the diamond back moth (Plutella xylostella), and the cabbage moth (Momestra brussicae). Several syntheses of 29 were achieved by means of Wittig chemistry,I2' organoborane chemistry,95-120 organotransition metal chemistry,79 and acetylenic chemistry.126A synthesis of 29 was reported by Tolstikov et al. starting from l-methyl-l,5-cyclooctadiene(Scheme 62).127 n

1) 0.9eq 0, 2) H, I Lindlar-P

( 60% ) H

H

H .. \

I

H ..

c=c

Me(CH,); LI,CUCI,

(~ 5 %

29

\(CH2),,0A~ 30

Scheme 62

L. (2)-11-Icosenyl Acetate 30 (C22H4202) This was identified as the aggregation pheromone in a By (Drosophila malerkotliana). This was not attractive alone, but was synergistic with fcrmenting food or with acetone. 128

7. PHEROMONE ALCOHOLS AND ACETATES WITH A CONJUGATED DIENE AND CONJUGATED ENYNE SYSTEMS Conjugated dien- 1-01s and their acetates are frequently encountered among pheromones. Bestmann et al. reported a general synthesis of such conjugated

38

The Synthesis of Insect Pheromones, 1979-1989

dienes with (E,E)-, (Z,Z)-, (2,E)-, and (E,Z)geometries essentially by means of Wittig chemistry.'29

A. (52,7E)-5,7-Dodecadien-l-ol 31 (C12H2,0) This is the female-produced pheromone of the pine moth (Dendrolimus spectubilis) and the forest tent caterpillar (Mulucosomudisstriu). The acetate of 31 is the pheromone of D. punctutus. A synthesis of 31 reported by Ando et al. utilized organozirconium chemistry to generate the @)-double bond (Scheme 63).I3O The final semi-hydrogenation, however, was not sufficiently selective (CH,),OTHP

to give a mixture of the starting enyne ( 5 % ) , the over-reduced monoenes (24%), and the desired diene (7 1 %). These were separated by chromatography. Rossi and Carpita synthesized 31 by the combination of organoborane chemistry and organopalladium chemistry (Scheme 64).1 3 ' Application of organo-

Me(CH,),CICH

'

"^'pqZ)3

'

3) 12, NaOH , EGO ( 53.5% )

'c = c' \I

HC=C(CH,),OH (Ph,P),Pd , Cul I C,H, (PhCH,)EbN' CI' , NaOH aq ( 70% )

( 95% )

Scheme 64

31

>

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

39

copper chemistry by Normant et al. led to an efficient synthesis of 31 (Scheme 65). 32 Ll

EEO(CH,),Br

EEO(CH,),LI

1) 0.5eq CuBr*Me,S 2) HCsCH

Scheme 65

A synthesis of 31 by Trost and Martin was an application of their alkynylsulfenylation reaction of olefins (Scheme 66). 1 3 3

Me(CH,),CH

= CH, +

Me(CH,),!HCH,C

SMe

I

SC(CH,),O&~

1 ) CF,SO,CH,CO,EII 2) DBU.46°C 3) (n.Bu),NF /THF ( 69% )

MeSS'Me,BF,'

+

I

H2'Undlar-Pd

I

hexane

>

H,

h(CH2);

H,

c = c'

THF (14:l) ( 53% )

,

Me(CH,),$HCH,\ SMe

( 99% )

MeCN

CICH,CH,CI

E q I C EC(CH2),0hj-

(CH,),O$f C=< H'

H

ti C=C' \(cH,),oH

k

31

Scheme 66

Organoborane c..:mistry as applied by Brown to the syn-..esis of 3- proved to be highly successful (Scheme 67).134 Stille and Groh prepared 31 by means of the palladium-catalyzed cross-coupling reaction of a vinyl iodide with a vinylstannane (Scheme 68).'35Another synthesis of 31 by Stille and Simpson utilized a palladium-catalyzed coupling of vinyl iodides with acetylenic tin reagents (Scheme 69). 136 Scheme 70 illustrates Huang's synthesis of 31.137This formylolefination of aldehydes by means of (formylmethy1)triphenylarsonium bromide in the presence of potassium carbonate gave (E)-a,P-unsaturated aldehydes ( >98% E) in excellent yields.

40

The Synthesis of Insect Pheromones, 1979-1989

Scheme 67

H

MCH&

ICEC(CH2),0H

K02CN-NCOzK

AcOH-WH (62%)

’ p= I

c:< I4 SnMe,

,H

c,

(CH,),OH

25%

31

Scheme 69

I DMF (73%)

PdCI,(MeCN),

7. Pheromone Alcohols and Acetates with Coqjugated Diem and Enyne Systems

(75%) 1) [Ph,P'(CH,),OAc]W

-

n.BuU/ THF HMPA 2) KOH /aq EIOH

41

>98% E

WCH~)S\ H C=C: (CH,),OH H' C=C'

d

(68961

k

31

Scheme 70

Recently Naso and co-workers published an efficient synthesis of 31 by combination of organocopper and organopalladium chemistries, starting from phenylthioacetylene (Scheme 7 1). 13*

1) Me(CH,)3Mg&

NiCI,(Ph,PCH,CH,PPh,) €50, room temp 2) TSOH/MeOH (77%)

WCHz),\

=

H

C C:

(CH,),OH C=C' H' \H 31 52.7E I 98% H'

Scheme 71

B. (SE,72)-5,7-Dodecadien-l-oI 32 (C12H220) This is the pheromone of the pine moth (Deitdrolinus spectrobilis). Stille's organotin chemistry with the aid of palladium catalysis yielded 32, as shown in Scheme 72.'36 HCIC(CH2),0THP

Me(CH,),CsCSnMe,

1) Cp,Zr(H)CI 2)

PdCI,o,

12

DMF ,25OC

( 85% )

( 95% )

Scheme 72

42

The Synthesis of Insect Pheromones, 1979-1989

C. (7E,92)-7,9-Dodecadienyl Acetate 33 (C 14H2402) This is the sex pheromone of the grape vine moth (Lobesia botrana). Langlois’s synthesis of 33 started from 2-picoline (Scheme 73). 139

( 57% overall )

H,

+

Me,NCH,

1’

\

H,

,(CH,),OTHP C=C

1) Me,CuU/THF

k

2) TsOHlMeOH 3) Ac,O I C,H,N

I

C=C

H‘

( 88% )

k

*

El

\

(CH@Ac C=C‘

I

c=c

k

H‘

k

33

(68%)

(7E, 92) : (7E. 9E) = 92 : 8

Scheme 73

A Grignard coupling reaction was employed for the synthesis of 33 (Scheme 74). I4O Preparation of (2E,42)-2,4-heptadien-l-01, the starting material, had previously been reported. 14’

H‘

\

,C=d

c=c

k

H

CH-OH

H

El\

k

<

A 5 0 / C,H,N

El

\

1

k

c=c

H‘

CH,OAc

\

I

C=C

\H

-

CIMg(CH,),OTHP LI~CUCI, I THF

Scheme 74

Linstrumelle prepared 33 by nickel- and palladium-catalyzed coupling reactions of Grignard reagents with vinyl chlorides (Scheme 75).’42

7. Pheromone Alcohols and Acetates with Codugated Diene and Enyne Systems U

H

GI\ CiC’

H’

+

H

>

Ni(PPh,),

CIMg(CH,),OTHP

E$O. CH ,,

\Cl

43

( 96% )

(33%)

Scheme 75

Rossi et al. employed the palladium-catalyzed coupling reaction of 1-alkenylborane with 1-bromoalkyne in their synthesis of 33 (Scheme 76). ‘43 (Sia),B, ECECH

>-

1) El!&&

EICPC-Br

21 Brz

’)

c:c:

H

H’

(CH,),QTHP

Pd(PPhJ,, NaOMe 2) Hz02,NaOH aq

EICfC,

/”

c =c

H’

‘(cH~),oA~

3) Ac,O/AcOH

( 47,6% )

1) (Sia),BH I THF

2) AcOH 3) H202, NaOH aq

>

(Q@/.)

Scheme 76

A similar palladium-catalyzed coupling reaction of 1-alkenylborane with (2)1-iodo-I-butene was used by Cassani et al. to prepare 33 (Scheme 77).’44

>

HCfC(CH,),OSiMe, THF

44

The Synthesis of Insect Pheromones, 1979-1989

Descoins et al. reported two syntheses of 33 employing organotransition metal chemistry. 145 In their first synthesis, coupling of (Z)-1-iodo- 1-butene and propargyl alcohol was followed by reduction to selectively give A (Scheme 78). ’45 However, the Grignard coupling of B and C caused isomerization at C9. H\

,H

+

C=C

El’

Pd(PPh,), / C6H,

HCICCH,OH

n-PfNH,, Cul

\I

,H

H, c=c,

>

E(

LiAIH,

THF

CECCH20H

( 82% )

(82% )

‘

A

1) CIMg(CH,),OTHP (C) CH20Ac

Li2CuCI, I THF 2) TsOH / aq MeOH

B

4

’

( 51% )

33

1

Scheme 78

The product was a 4 : 1 mixture of 33 and its (7E,9E)-isomer, which had to be separated by preparative HPLC. The second route (Scheme 79) was more selective than the first. 14’ CI,

C=C

H’

,H ‘CI

33

+

CIMg(CH2),OI.Bu

Ni(PPh,), C6H8-Eb0 ( 65% )

’ ‘I,

$=d\lCH,),Ot-BU

HCIO, / AcOH

(98%)

Scheme 79

Normant’s organocopper chemistry was used for the synthesis of 33 and proved to be quite efficient (Scheme 80). 132 Alexakis and Jachiet also employed organocopper chemistry to prepare 33 (Scheme 8 1). ‘46. ‘47 Alexakis developed

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems 2eqHCrCH CuLi

( 78% overall )

33

H H “ c=c El’ ’znX

+

ZnBr,

El’

45

Cu. UX

( EZ = 97.3% )

Scheme 80 1) Li

I-BuO(CH,),Br

[l-BuO(CH,)J,CuLi

H, c=c‘

2 Na

1) HCsCH

21

12

E;c:c\

H\

ti

I.BuO(CH,)~

‘I

c=c’

0

MCPBA CH,CI,

H“ Me,Si (CH,),OI-Bu cis-puriiy >99%

1 45% overall )

(

’

’

CuLi

LiBr , BF, EbO

M)’C ,30min

a new method for the preparation of w-hydroxyalkenyl iodides via hydroalumination-iodination of w-r-butoxyalkynes, and used the method for the synthesis of 33 (Scheme 82). 14’ I-BuO(CH,),CrCH

1 ) (i-Bu)filH / hexane 2) I,/ THF

3) Ac,O, FeCI,/ €50 ( 55% )

’

( 92% overall )

Scheme 82

H

I

A

33

( E Z >99%)

46

The Synthesis of Insect Pheromones, 1979-1989

2) Ph,P / CH,CI,

OHC(CHp)SC02Me

Ph3P-CHCH0 ( 26% )

Scheme 83

Bestmann et al. synthesized 33 by Wittig chemistry (Scheme 83).'49 A synthesis of 33 by a Wittig route was also reported in connection with the effect of isomeric purity on pheromone activity (Scheme 84). 150 A combination of ace-

HCfCCH,OTHP

33

+

Br(CH,),OTHP

n-BuLi

THPqCH,),CTCCH,OTHP

1) n.BuLi 2) AcOH

'

Scheme 84

tylenic and Wittig chemistries allowed a large-scale preparation of 33 (Scheme 85).15' Julia's sulfone chemistry was applied to the synthesis of 33, although the overall yield was modest (Scheme 86). Is* Phenylthioacetylene was found to be a good starting material for the synthesis of 33 (Scheme 87).13* The ultraviolet absorber, 2-hydroxy-4-methoxybenzophenone,and the antioxidants, BHT and BHA, were found to be effective in solution as the chemical protectors of pheromones with the conjugated double-bond system from isomerization and oxidation. 153

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

+

1) MeMgCI/THF

HC P C(CH2),CI

2) CH(OEI),

1) H2/ P-2Ni

(EIO),CHC I C(CH,),CI

2) 20% HCI / CH,CI,

toluene

( 90.3% )

(71%) H\

c=c‘

OHC’

(CH2)6C’

B i / THF

[Me(CH,),P’PhJ I-BuOK

KOAc / AcOH i60°C,7h

>

H\ C=C El’

,H

El‘

H

\C=C‘

H’

( 92% )

H\ C=d H \C=C‘ H’ \(CH,),CI

>

( 63.3% )

\H

( E >QQ% )

>

\(cH,),oA~

33 [ conlg. 13% (E. E)-isomer]

Scheme 85

+

CH,(SO,Ph),

Q

OHC(CH,),OTHP

,AcOH

>

AI-Hg

=

(PhSO,),CHC H f$CH,),OTHP

(84%)

( 85% )

PhSO,CH,C

H

=C(CH,),OTHP

H

2) ECHO 3) Ac,O

OAc

>

H

1) NaOH / EhO

EI~ICHC C(CH,),OTHP b2PhH

2) SO, chromalog. ( 25% )

( 75% )

/W,Ph

H, C=C

El‘

H

1) Ni(acac), n-BuMgCI

\(CH,),OTHP

2) HCI. MeOH 3) A~,O

%=C‘

H‘

H\C=C’

>

El‘

33

( 38% )

H

\C=C: H’ (CH,),OAc (7E,92)=95.1?4

Scheme 86

PhSC p CH

-.

-50% room temp ( 85% )

,

H\c=d

Et’

”=(

H‘

H\ C-C’ H El’ ‘C=C’ H’ ‘(cH,),oA~ 33

(EZ-97X)

Scheme 87

ti SPh

1) E E O ( C H 2 ) e Y ~ NiCI, (Ph,PCH,CH,PPh,) 2) TsOHlMeOH

3) A%O/CCSH,N ( 78% )

/ THF - EGO

>

47

48

The Synthesis of Insect Pheromones, 1979-1989

D. (8E,10E)-8,10-Dodecadien-l-ol 34 (C12H220) This is the sex pheromone of codling moth (Luspeyresia pomonella). Organosulfur chemistry was utilized for the synthesis of 34 by four groups. Thermolysis of allylic sulfoxide A to 34 was reported by Babler and Haack (Scheme 88). 154 Alkylation of 3-sulfolenes was the key reaction in Yamada’s synthesis of 34 (Scheme 89). Double alkylation of sulfone A to give B was followed by its thermolysis to give 34 (Scheme Julia used his sulfone chemistry for the synthesis of 34 (Scheme 91).15*

A

I(CH2),0THP LiN(SiMe,),

0,

(58%)

>

-a*,8 34

Scheme 88

0

(CH2),0THP

LiN(SiMe,),

( 5596 )

0 2

Scheme 89

M

e

34

H

(EE=96.3%)

Scheme 90

(CH,),OTHP

0 2

( conlg. 10% of &isomer

)

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

49

1) NaH / DMF H CH.Br

,

1-70

34

/

Scheme 91

Sat0 et al. synthesized 34 employing the ester enolate Claisen rearrangement of ( E ) -1 -methyl-3-trimethylsilyl-2-propenyl glycolate followed by the Peterson reaction (Scheme 92). '59 0

HOCH,

- %.o '

.,

1) LiN(SiMe,), 2) Me,SiCI

3) CH,N,

2) Ac,O

>

H,

H,

'

c=c'

(62%)

'CzC'

M/

(93% )

1) UAIH,

Me,Si$ C0,Me H C-C'

C =C'

CH,OAc

k

H,

CO 'H H '

1) CIMg(CH,),OTHP,

KH/THF

H,

-78'--4OoC> (89%)

Mel

Cul

2) H' ( 67% )

>

Cope C=C'

C=C:

H,

H,

C=C'

Mel

C=C

k

k

/(CH,)+H '

\H 34

Scheme 92

E. (82,10E)-8,10-Dodecadien-l-ol35 (C 12H220) Hedya ochroleucana employs this dienol 35 as its pheromone. A synthesis of 35 by Sat0 et al. started from A (Scheme 93), which was prepared as shown in

A

H,

Me'

H\C=C:

C=C'

k

6 2Z1,4E:2E, 4E :22,42 .go: 3 ; 7

( 89% )

ClMg(CH2)rO&Cl, Cul CH,OAo

(23?4tMlS)

Scheme 93

H\

Me'

c=c'

C=C'

k 35

" \(cH~),oH

50

The Synthesis of Insect Pheromones, 1979-1989

Scheme 92. 159 The selectivity to generate (22,4E)-B, however, was not satisfactory. A synthesis of (82,1OZ)-8,1O-dodecadienylacetate by palladium-catalyzed coupling of an organozinc compound and 1-iodo-1-alkene was reported by BjorHing et al.16"

F. (E)-9,11-DodecadienyI Acetate 36 (C14H2402) The female-produced sex pheromone of the red-bollworm moth (Dipuropsis cusfunea) is a mixture of 9,ll-dodecadienyl acetate ( E : Z = 80:20), (E)-9dodecenyl acetate, 11-dodecenyl acetate, and dodecyl acetate, Two syntheses of 36 were based on Wittig chemistry. Bestmann et al. prepared 36 as shown in Scheme 94.149Ranganathan et al. synthesized 36 starting from Indian castor oil (Scheme 95). I6l Methyl ricinoleate A, prepared from

38

(E:Z-06:4)

Scheme 94

Indian

castor oil

NaoMe M~OH

C0,Me

>

(48% )

( 85% )

6H

( 84% )

( 80% )

H,C=CH(CH,),CO,Me

A

8

36 ( E : 2 - 9 8 . 3 : 1 . 7 )

Scheme 95

TSOH ( 66% )

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

51

castor oil, was convened to the key-intermediate B,Cf.16* and then to the pheromone 36 in 11.6% overall yield from castor Snider and Phillips used an ethylaluminum dichloride-catalyzed ene reaction of formaldehyde with 10-undecenyl acetate for the synthesis of 36 (Scheme 96). 163

( 72% )

(E:2=78:22)

36

( 65% )

Scheme 96

Several syntheses of 36 were based on sulfur chemistry as follows. A synthesis of 36 was accomplished in 44% overall yield from 3-sulfolene in the same manner as for the synthesis of 34 (cf. Scheme 89). 15', 156 Ochiai et al. synthesized both ( E ) - and (Z)-9,1l-dodecadienyl acetates via phenylsulfones by lengthy routes (Scheme 97). '61

H,

n-BuLi , TsCI , LiCl

Ebo-HMPA

'CICH,'

c.d

(CH,),OTHP

(CH,),OTHP

k

L

( 67% )

( 98% )

H\

c=cf

CH,

=ck

37

\(CH,),OAC

Scheme 97

52

The Synthesis of Insect Pheromones, 1979-1989

Hayashi et al. prepared pure 36 starting from ally1 dithiocarbamate (Scheme 98).165

H\c = c/(CHz)aoTHP

1) PPTSl MeOH

k

CHz=Ch

2) Ac,O/C,H,N

’

H

‘c = c’

k

CH2=Ch

(95%)

(CH,),OAo

36

Scheme 98

Schechter employed (E)l-benzenesulfonyl-4-trimethylsilyl-2-butene for the construction of the (E)-1,3-butadienyl part of 36 (Scheme 99).166

-

1) CH,=CHCHO 2) H,O+

Me,SiCH,WCI

>

OH

I

Me3BCH2CHCH=CH,

( 95% )

( 65% )

H,

CH,SOPh

c=c/

Me,SiCH;

H ‘

E:Z=9:l

H CH,=Ch

c‘ = d

MCPBA

(87%)

1) n B u L i

2) PhSCl

H\

CH2S02Ph

c=c/

Me,S~iCH;

k

’

1) n-BuLilTHF 2) Er(CH,),Br/

HMPA

>

( 94% )

(CH,),OAc

k

36

Scheme 99

The “ene” reaction of methyl 10-undecenoate with p-chlorophenylthiomethyl trifluoroacetate was the key-step in Ishibashi’s synthesis of 36 (Scheme loop7 Julia’s sulfone chemistry (Scheme 91) was also used for the synthesis of (E)9,ll-dodecadien-1-01.

7. Pheromone Alcohols and Acetates with Codugated Diene and Enyne Systems

CI O

S -

M

I1

(CF,CO),O CH,CI, (quanl)

e

0

>

36

(~ 5 %

CH,=CH(CH,),CO,Me

CI ~ S C H ~ O C O C F ,

CF3C02H ( 83% )

53

>

(E:Z=Bl:l9)

Scheme 100

Otera and his co-workers synthesized 36 employing methoxy(pheny1thio)methane as the initial building block (Scheme 101).l6*

(67%) I) (n-Bu),NF / THF 2) A c p / C,H,N

'

H,

c =c'

k

CH2=Ck

( 66% )

(CH,),OAc

36 ( E > 9 5 % )

Scheme 101

Organoselenium intermediates were used by Yamamoto et al. to prepare 36 (Scheme 102).'69 1) LDA/THF

2)

CH, =CHCH,SePh

3) AcO(CH,),CHO

>

PhSaOH CH, =CH&H&H(CH,),OA~

( 70% )

38

(E:Z=84:16)

Scheme 102

TsOH ( 77% )

The Synthesis of Insect Pheromones, 1979-1989

54

Rossi et al. reported a palladium-catalyzed synthesis of (E)-36 (Scheme 103).143 Diene-iron carbonyl complex was used for the synthesis of 36 by Knox HC PC(CH,),OTHP

ti, CH,

c=c'

=Ck

> ?

(CH,),OTHP

H,

-

k

(Sia)zE'

H,

A@

AcQH

H '

(CH,),OTHP

c=c'

(Sia) EH THF , Me,S

c=c'

CHZ=Ch

36

1) CHpCHBr, Pd(PPh,),

2) AcOH ,heal

, NaOH

>

3) H202, NaOH

(CHzlnOAc

k

(E>97%)

Scheme 103

and Thom (Scheme 104).I7OSeveral other pheromones such as 35 were also synthesized by this method.

q

>

CICO(CH2),C0,EI

Fe(CO),

TZ(CH2)6C02EI

AICI,

LiAIH, AICI,

FelCO),

>

(CH,),OH FelCO),

(ern)

( 70% )

G. (2)-9,11-Dodecadienyl Acetate 37 (C14H2402) Ochiai et al. prepared 37 by means of organosulfur chemistry (Scheme 97).'@ Palladium-catalyzed reactions were used by Rossi et al. for the synthesis of 37 (Scheme 10517' and Scheme 10617*). Michelot also prepared 37 by a similar coupling reaction. 'I7 8r(CH2),0THP

1) LiC-CH / H,N(CH,),NH,

, DMSO

2) H,O

>

HC EC(CHZ),OTHP

( 75% )

I ) EIMgEr/THF 2) CHz=CHBr, Pd(PPh,), 3) H,O 4) ACO , l AcOH 166% )

CH, = C H CIC(CH(,),OAc

1) (Sia),BH / THF 2) AcOH

3) H 2 0 2 ,NaOH ('1 ( 76% )

'

CH, = C k 57

Scheme 105

lCH,),OAc

/ CH ,,

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

CH, :CH&

+

Pd(PPh,), , Cul 10% NaOH ,CH ,, HCEC(CH$&'H

>

PhCH,N'E$C'

AcCl

Ch, =CHCEC(CH,),OH-

CAN

(97% )

( 74% )

CH,

= CH C D C(CH,)BOAc

1) (Sia),BH / THF 2) AcOtl

3) H202. NaOH

55

H

'

H

CH, =Ck

[ 76% )

(CH,),OAc 37

Scheme 106

H. (32,5E)-3,5-TetradecadienylAcetate 38 (C16H2802) This is the sex pheromone of the carpenter worm moth (Prinoxystus robiniae). Rossi et al. synthesized 38 by a palladium-catalyzed reaction (Scheme 107). Pd(PPh3), , Cul H, C = CI I

k

M~(cH,),'

f

H,

10% NaOH , CH ,,

HCEC(CH,),OH

PhCH,NE\CI

c=c'

Me(CH,);

( 85% 1

H '

( 73% )

( 97% )

C Z C(CH,),OH

38

Scheme 107

By employing their stereoselective formylolefination method with triphenylarsonium ylide, Huang et al. synthesized 38 (Scheme 108).137Preparation of Me(CH,),CHO

+

[Ph+'CH,CHO]Bi

&CO,/

baca H 2 0

1) [Ph3P'(CH2),0THP]Bi n-BuU / THF HMPA

.

H,

EGO. THF ( 7 :3 )

H\ H\ C I= d \ C=C (CH,),OH

2) HCI / eq MeOH ( 78% )

k

Me(CH,),'

H, Ac20

C&H,N (97%)

Scheme 108

,CHO

c=c

'

Me(CH,);

H\ C, =C: C

=C

H '

38

(CH,),OAc

The Synthesis of Insect Pheromones, 1979-1989

56

(3Z,5Z)-5-fluoro-3,5-tetradecadienylacetate, which enhances the pheromone activity of 38, was reported by Camps et al. 173*'74

I. (9E,llE)-9,ll-TetradecadienylAcetate 39 (C 16H2802) The light-brown apple moth (Epiphyas postwittuna) uses 39 as its pheromone component. This was synthesized by the sulfone alkylation-thermolysis route (Scheme and also by employing a 1,3-diene-iron carbonyl complex (Scheme 109).I7O

Scheme 109

J. (92,11E)-9,1l-TetradecadienylAcetate 40 (C I6H2802)

This is the pheromone of the cotton leafworm (Spodopteru lituru) and the Egyptian cotton leafworm (S. littoralis). Langlois's synthesis of 85% pure 40 started from 2-ethylpyridine (Scheme 110). 175 Bestmann's Wittig chemistry also led to the preparation of 85 % pure 40 (Scheme 111). 149 Me

*Me

I ) Me1 I MeOH

KOH aq

2) NaBH,

H,

El'

H H 'C=C:

c=c'

k

(CH2)70THP

1) TsOH I MeOH 2) AczO/C,HeN ( 65% overall )

>

H H 'C=C: C=C' (CH,),OAo EIl 40 ( E . Z : E . E - & 5 : l J ) H,

Scheme 110

k

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

57

40 (Z,E : E.2 :Z,Z:E.E I85.5:2.5:4.0:8.0)

Scheme 111

In the synthesis of 40 by Cassani et al., the intermediate A could be purified by recrystallization, and 95% pure 40 could be prepared (Scheme 1 l2).I4O

Palladium-catalyzed syntheses of 40 were reported by Linstrumelle (Scheme 1 13),’76Rossi (Scheme 1 14),143Normant (Scheme 1 15),’32 and Norin (Scheme

116).17’

.

.

Scheme 113

Scheme 114

5j ACCI I C&,N (SO % overall)

Scheme 115

40

58

The Synthesis of Insect Pheromones, 1979-1989

Scheme 116

A nickel-catalyzed reaction was used by Naso and his co-workers for the synthesis of 40 (Scheme 1 17).13*

Scheme 117

Julia's synthesis of 40 was based on his sulfone chemistry (Scheme 1 18).'52*'78kadav et al. prepared 40 via an acetylenic route (Scheme 1 19).'79

H,

PhY* H C=C: C=C'

E,'

k

1) n4uMpCI Ni(acac),lTHF

(CH2)nOTHP

H > ,=C;

3)A%O (37%)

Scheme 118

H H 'C=C: (CH,),OAO 40 (rW%pure)

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems H,

,CH,OH

c = c,

HC~C'

H

&(CH,),OTHP' (72%) H

THPO(CH,),CEC'

H,

LiNH, / NH,

CH2CI H

THPqcH,),Czc'

Ph,P / CCI,

H

(65%)

El

H

'c = c'

MMl,CUl (WW

,CH,OH

c = C,

THPO(CH,),CSC

,

> -

H

59

'

1)TsOH/ MeOH 2)Ac20/CgHgN (61%)

40

Scheme 119

K. Bombykol [(10E,12Z)-10,12-Hexadecadien-l-ol]41 (C16H300) This is the well-known sex pheromone of the silkworm moth (Bombyx mori). Normant reported an organocopper-based synthesis of 41 (Scheme 120). The

41 (10E,l22 =80%)

Scheme 120

second organocopper-based synthesis with concomitant use of palladium-catalysis was also reported by Normant (Scheme l2l).I3*The third organocopper-

Scheme 121

60

The Synthesis of Insect Pheromones, 1979-1989

based synthesis was reported by Alexakis and Jachiet (Scheme 122). 1 4 6 s 1 4 7Naso's combination of organocopper and organotransition metal chemistries resulted in an efficient synthesis of 41 (Scheme 123).'38 H

/

l)EEO(CH,),MgBr/EGaTHF

H

41 (97% pure)

Scheme 123

-

Hydroalumination of 1-(trimethylsilyl)-l,3-diyne was employed to construct the (E)-olefinic system of 41 (Scheme 124). 1 8 ' THPo(CH,),CrC-CrCSiMe,

H,

Me(CH,),C

c.c'

c'

l)Li[n-BuAI(i-Bu),H] I DME _____3

2) dil HCI 3)KF*2H20/ DMF

(CH,),OTHP

k

1) (Sia),BH 1THF 2) AcOH I6O'C

3) HzOz,NaOH 4) HCI / MeOH

H,

THPO(CH,);

'

F e C H n-BuLi/hexane k b(CH,),Br 1W m e

czc

H H 'C=C' \

I

H

c=c

4

'(cH,),oH

41

Scheme 124

Bombykol (41) was also synthesized by means of organoborane chemistry. Suzuki and his co-workers used their palladium-catalyzed cross-coupling reaction between alkenylboranes and 1-bromoalkene to prepare 41 (Scheme 125). 1 8 2 * 1 8 3 (Z)-1-Iodo-1-alkenes can be conveniently prepared as shown in Scheme 126.'84(Z)-1-Iodo-1-pentene can be a precursor to 41. Bombykol (41) could be prepared by a palladium-catalyzed cross-coupling reaction between an alkenylboronate and 1-iodo-1-alkene (Scheme 127). Trost's palladium-catalyzed decarboxylative elimination reaction yielded bombykol of about 90% purity (Scheme 128).'86 Ishibashi's "ene"-type reaction previously yielded a thioether A (Scheme 129; cf. Scheme loo), which was converted to 41.18'

61

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

H H ‘C=d H / \ / Me(CH,), C =C, (CH,),OH

d

-

( E , Z : E , E =96:4)

41

Scheme 125 HBBr,-Me,S

R-CEC.Br

>-

“C H’

=!C

B

Me2CHOH

\BBrl.SMe,

’

c=c’

H’

Br

KB(OCHMe,),H

\B(OCHMe2),

Scheme 126

41

Scheme 127

41

(E.22 98%)

(E,ZP,Z -e:i)

Scheme 128

C

l

NCS

O S(CH,),CH=CH(CH,),CO,Me A

OHCCH,CHmCH(CH,),CO,Me

HCI MeCN (86%)

’

H,

I(CHZ)&02h!+’

c=c,

OHC‘

Scheme 129

known

CuO. CuCI,*PH,O aq Me,CO (60% from A)

’

62

The Synthesis of Insect Pheromones, 1979-1989

A combination of zirconium-mediated [2,3] Wittig rearrangement and Peterson reaction allowed Kuroda et al. to prepare the key (E,Z)-diene system of 41 (Scheme 130).’88 I) BrCH,COzH, base Iss3siT

2) i.Prl, base (87%)

1) DHP. PPTS

?H

tl LDA

O H (CH,),Me

Me,Si qO,CO,i.Pr

>

(%),Me

OH

Tsuboi et al. discovered a rearrangement of allenic esters to (2E,4Z)-dienoic esters with alumina catalyst, and used that reaction for the synthesis of the (E,Z)-diene portion of 41 (Scheme 131).’89*’90 H

OH

I

MeC(OE1)3

Me(CH,),CHCECH

EICO,H,

A1201 Me(CH,),CH=C=CHCH,CO,EI

heal>

(69%) >Me(CH,);

(76%)

UAiH, (89%)

3

Me(CH,),

/

,” C=C \

H\C:C‘

H \C=C‘ H’ \CO,Et

2E.42 z 93% 1

H

C =C H’ ‘CH,OH

3

41

__3

Scheme 131

A synthesis reported by Stille and Simpson employed their palladium-catalyzed reaction of a vinyl iodide with an acetylenic tin reagent (Scheme 132).19’

Scheme 132

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

63

L. (11Z,13E)-11,13-HexadecadienylAcetate 42 (C18H3202) This is a potent pheromone component in some processionary moth species. Alexakis and Duffault synthesized 42 by coupling (E)-1-butenylzinc bromide with a (Z)-1-iodo-1-alkene (Scheme 133).14*

I ) (i.Bu)#IH

EICZCH

(63%)

H,

c=c:

E'l

I

H'c=c'I

El'

'H

H$

l)n.BuLi/E$O

E,'

2)ZnBr2/THF

C=C

pBr c-C> H

H' (86%)

Scheme 133

,(CH,),,OAc 'C = C HI 'H 42 (Z,E > 99.7%)

M. (Z)-ll-Hexadecen-13-ynylAcetate 43 (C18H3002) This is a plausible component of the sex pheromone of the oak processionary moth (Thaumetopoeaprocessionea). Camps et al. reported a synthesis of 43 by means of organopalladium chemistry (Scheme 134).19*A new method to con-

I ) NBS/ E$O.C,H,N:

hv

k

(80%)

I ) PdCI,(PPh,),

/THF

(i-Bu)#lH, Cul. n-PrNH, 2) EICECH 3) TsOH / MeOH (82%)

-

H\ I(CH2)100THP CnC

Ma3Si'

Acp

H\

>

c=c'

EICEC'

1) Br,/CH,CI,

\(CH2),,0H

H,

C5H5N (95%)

IICH,),oOTHP C2C

2) NaOMe IMeOH (74%)

B:

H '

c = dti

H\ ECSC'

\(cH,),,oA~ 43

Scheme 134

struct the (Z)-l-en-3-yne system of 43 by ring cleavage of a P-halogeno ether with samarium iodide was reported by Crombie and Rainbow (Scheme 135).193 Sml, (4-7eq)

> \OH

~ ~ ~ , r e ~ u x 5-165hr (93%)

Scheme 135

> 97% 2

64

The Synthesis of Insect Pheromones, 1979-1989

N. (Z)-13-Hexadecen-ll-ynylAcetate 44 (C 18H3002) This is the female-produced sex pheromone of the processionary moth (Thaw metopoea pityocampa), a major defoliator of pine trees in Mediterranean countries. The first synthesis of 44 was achieved by Camps et al. as shown in Scheme 136.Ig4 OH

,,

1) TsCl

1) n-EuUITHF-HMPA

distillalion

Scheme 136

Michelot et al. reported a palladium-catalyzed synthesis of 44 (Scheme 137).' 9 5 Scheme 138 illustrates the second palladium-mediated synthesis by Rossi and Carpita. '96 Stille's third palladium-mediated synthesis utilized an organotin intermediate (Scheme 139).1 9 '

2) NaHCO, / DMF

(38%)

6

94

CI(CHz)BOTHP

Mg ITHF 2) Er(CH,).Er _. Li2CuCI,

>

Er

H,

>

Er(CH2),oOTHP

>-.

NH.-DMSO

HC=C(CH2),,,0THP

(53%)

(79%)

Cul, n-PrNH, / C,H, (79%)

Scheme 137

44

7. Pheromone Alcohols and Acetates with Conjugated Diene and Enyne Systems

65

(78%)

(38%)

H\

c=c'

AcCl C5H5N

El'

(98%)

44

\C~C(CH,),,OAc (98% pure)

Scheme 138 1) n&U. Me(CH,15Br 2) PPTS / EtOH

HCrC(CH,),OTHP

1) UAPA

Me(CH,),C=C(CH2),OH

2) Ac20 (93%)

(65%)

HCrC(CHz),,OAc

H

H

El'

\I

c' Ic'

>

Me,SnNEL, (76%)

Me,SnCtC(CH,),,OAc

H, c z c : El'

CZC(CH,),,OAo

(86%)

44

Scheme 139

>

Normant's organocopper chemistry was successfully applied to synthesize 44 (Scheme 140).19' Et2CuLi

EZ&<E:c:cq

3 2 CULl

H\C Z d ~ t '

\cu,Lil

THF

1) UCsCH / THF. DMSO

Br(CH,),,OH

IC=C(CH2),,0Ac

*)

3)1z'

> c\'f:

TMEoA (76%)

Et'

C ' rC(CH2),,0Ac

o3H,lolueneZ (69%)

Scheme 140

Shani et al. '98 and Camps et al. '99 synthesized 44 via almost similar routes, by employing acetylenic intermediates followed by Wittig olefination, Scheme 141 shows the synthesis by Camps.'99

Scheme 141

66

The Synthesis of Insect Pheromones, 1979-1989

8. PHEROMONE HYDROCARBONS, ALCOHOLS, AND ACETATES WITH A NONCONJUGATED DIENE SYSTEM General synthetic methods for 1,4-, 1,5-, and 1,6-alkadiene pheromones were reported by Bestmann et al., based essentially on Wittig chemistry.200.20’

A. (32,62)3,QNonadecadiene 45 (C19H3,j) This is a pheromone component of geometrid moths (Geomerriidue). Nikolaev and Kovalev synthesized 45 as shown in Scheme 142.202

B. (32,62)-3,6-Henicosadiene46 (C2,Hd0) This is a pheromone component of tiger moths and allies (Arctiidue) and was synthesized by Nikolaev and Kovalev in the same manner as for 45 (Scheme 142).202

C. (62,92)-6,9-Henicosadiene47 (C2,H40)

This is the EAG active diene found in the sex-attractant secretion of an Arctiid moth (Utetheisu ornurrix). Meinwald et al. synthesized 47, starting from ethyl linoleate (Scheme 143).203 H MepH,),

HH, H CEI / \ CH, (CH,),CO,EI

‘c:d\

I

47

4 -

H,

c:c

(83%)

Me(CH,):

Scheme 143

,HH,

,H

‘Ck;

\(CH,),OTS

c-c

[Ms(CH,),J,CuLi

(99%)

8. Pheromones with a Nonconjugaled Diene System

67

D. (72,112)-7,1l-Heptacosadiene48 (C27H52),(72,112)-7,1l-Nonacosadiene 49 (CZ9Hs6),and (72,112)-7,1l-Pentacosadiene50 (C25H48)

The major sex pheromone of the fruit fly (Drosophila melanogaster) was identified as 48. The minor biological activity was associated with 49 and 50. Davis and Carlson synthesized 48, 49, and 50 employing the coupling reaction of dihydropyran and Grignard reagents under nickel catalysis as the key-step (Scheme 144).'04

Langlois achieved a synthesis of 49 by utilizing a silicon-induced fragmentation, a coupling reaction with a Grignard reagent, and a Wittig reaction (Scheme 145).'05

(74%)

A

Scheme 145

The Synthesis of Insect Pheromones, 1979-1989

68

E. (4E,72)-4,7-TridecadienylAcetate 51 (Cl5Hz6OZ) The potato tubenvorm moth (Phthorimaea operculella) uses 5 1 as the femaleproduced sex pheromone. SN2'-type reaction of y-vinyl-y-butyrolactone with an organocopper reagent was employed by Fujisawa et al. for the synthesis of 51 (Scheme 146).*06

Scheme 146

In Yadav's synthesis, a Grignard coupling was followed by alkylation of an acetylenic alcohol to give 51 (Scheme 147).2"7 H\

c =d

MsCI, LiCl

1) Me(CHZ)3MgBr/El$

H,

c=c 'CH,OCH,Ph

1) U / NH, 2) PBr3/ E$OG,H,N

>

(75%)

Scheme 147

Nishiyama et al. employed a Beckmann fragmentation of a cyclopentanone oxime to prepare 51 (Scheme 148).208

H . Yamamoto and co-workers synthesized 51 by highly stereocontrolled Claisen rearrangement using an organoaluminum reagent (Scheme 149).209*2'0

8. Pheromones with a Nonconjugsted Diene System

Me(CH2),CtCH

1) n.BuU I THF 2) BrCH,CH(OEI),/ ( 5 ~ 4

HMPa

Me(CH,),CaCCH,CH(OEI),

69

H, 1 P.2 Ni H,N(CH,),NH~ EOH

Scheme 149

F. (2)-5,13-TetradecadienylAcetate 52 (Cl6Hz8O2) This is the pheromone of the European goat moth (Cossus cossus). 52 was synthesized by Normant et al. by alkjlation-of an organocopper reagent (Scheme 150) I

'

.

.

52

Scheme 150

G. (92,12E)-9,12-TetradecadienylAcetate 53 (C 16H28O2) This is the pheromone of the southern armyworm moth (Spodoptera eridiuna), the almond moth (Cedru cautella), the Indian meal moth (Plodin interpunctella), and several other Lepidopteran insects. A synthesis of 53 by Bac and Langlois employed a fluoride ion induced silicon fragmentation of a tetrahydropyridinium salt (Scheme 151).2"

Scheme 151

The Synthesis of Insect Pheromones, 1979-1989

70

Mandapur prepared 53 by means of classical acetylenic chemistry (Scheme

‘*

152).

H, HOCH:

(CH&OTHP

CH

c=c’ %=c‘

!-I6

H ‘

H,

1) MsCl I EL,N 2) LiAIH,

>

3)AcCt/AcOH (79%)

,Cyz

c=c

c=c’

’H H’

Me‘

(CH,),OAc

k

53

Scheme 152

H. (6E,llZ)-6,1l-HexadecadienylAcetate 54 (C18H3202) This acetate 54 and (6E,112)-6,ll-hexadecadienal were isolated as the pheromone of the wild silk moth (Antheraeapolyphemus). Bestmann and Li synthesized 54 by a combination of Wittig chemistry and organoborane chemistry (Scheme 153).’13 Another synthesis of 54 as reported by Wang and Chu utilized

Me(CH,),CH-PPh, +

OHC(CHZj3OTHP

Ph,P-CH,

p = c,,H

H,

OoH-

Me(CH,),

>CH,-CH(CH,),OTHP

BH

(CH,),OH

PCC (7%

*

B[(CH,),OTHPJ,

Scheme 153

an intramolecular transfer reaction of lithium I-hexynyltrialkylborate as induced by tri(n-buty1)tin chloride (Scheme 154).*14

8. Pheromones with a Nonconjugated Diene System

71

I. Gossyplure, a Mixture of (72,l 12)-7,11-Hexadeeadienyl Acetate 55 and Its (7Z,llE)-Isorner 56 (C18H3202) Six new syntheses of 55 and 56 were reported since mid-1979. Leznoffs solid-

phase synthesis was applied to the preparation of 55 (Scheme 155).*15 The

(62%)

55 (15% overall yield)

Scheme 155

polymer support employed was 1% or 2 % styrene-divinylbenzene co-polymer containing trityl chloride groups. This unique synthesis of 55, however, was not very efficient. A cyclic phosphonium ylide was used to prepare a mixture of 55 and 56 (Scheme 156).2'6By carrying out the Horner reaction in a 1 : 1 mixture of THF and ether, it was possible to obtain the desired ca. 1 : 1 mixture of 55 and 56, which is active as the pheromone of the pink bollworm moth (Pectinophoru gossypiella). Joshi et al. synthesized gossyplure by a combination of an acetylenic route and Wittig chemistry (Scheme 157).2'7 They also prepared 55 and 56 separately, employing aleuritic acid as the starting material (Scheme 158).2'7

8. Pheromones with a Nonconjugated Diene System

73

1 : 1

diastereomerio ratio = 1:l

Scheme 159

NaGCH Br(CH,),b

xylerm.AcNMez

KOBr

HCnC(CH,),Br

Me(CHz),CH=CH(CHz)2C-C(CH,)eB~

+ BrC=C(CH,),Br (81%)

KOAc / AcOH 17OoC, 3hr (95%)

2) CuBr (75%)

Me(CH,)3CH=CH(CH,),C&(CHz),0Ac

>

' a/ HZ pd-Bas04

>

MeOH

(98%)

chemistry and furnished a 1 : 1 mixture of 53 and 56.*19Their process is employed by Shin-Etsu Chemical Co. for the production of gossyplure. Michelot synthesized 55 by organopalladium-catalyzed cross-coupling reaction (cf. Scheme 54)."' (72,11E)-7,1l-Hexadecadienylacetate (56) is the sex pheromone of the Angoumois grain moth (Siforroga cerealella). Kang's synthesis of 56 employed the Julia cleavage (A -+ B) as the key-step to generate the (,!?)-double bond (Scheme 161).220

Scheme 161

74

The Synthesis of Insect Pheromones, 1979-1989

J. (2E,132)-2,13-Octadecadienyl Acetate 57 (C20H3602)

Isolation of the sex pheromone of the grape root borer (Vitacea polistiformis) was carried out by Schwarz et al. using only seven female insects. The pheromone was identified as 57 and synthesized as shown in Scheme 162.22'

Me(CH2),C.CCH20H

>-.NaH

> -DHP H'

HC=C(CH2)oOH

H,N(CHJ,NH,

Me(CH2),C-C(CH,),Bf

1) MeLi /THF-HMPA

Me(CH,),Br

2) Ph,PBr,

LiC=CCH20THP THF-HMPA

1) LiAIH,.NaOMe(l:2) 2) A%O / CH ,N , 3)H2/P-2Ni

HI

MeICH,),

,H

p ::c,

/ CH2CI,

Ac20

> Me(CH2),CsC(CH,),C.CCH20THP

Me(CH2),C=C(CH2)oCaCCH20Ac

-

HC.C(CH,),OTHP

-,

AcOH

H,

,CH,OAc

C=C (CH2),/

'H

57

Scheme 162

The leopard moth (Zeuzera pyrina) also secretes 57 as its pheromone, which was synthesized by the acetylenic route (Scheme 163).222Descoins also syn1) LiNHz/NH, Me(CH,),C&H

2) L(CHz),OTHP

1) H,O'

> Me(CH,),C=C(CH,),OTHP

2) H, / P-2 N'i 3) Pb,

H, Me(CH,);

c.c'

1) UAIH, / THF '(CH,),C%CCH,OH

2) Ac,O/ CH ,N ,

H,

,H

c=c

\

(CH,),/

H,

WCH,),

p = c,

1) LiCrCCH OTHP /THF-H&PA (CH,),Br

2) H@'

,CH20Ac

c=q

H

57

Scheme 163

thesized 57 by a combination of an organopalladium-catalyzed process and acetylenic chemistry (Scheme 164).223 Both a clearwing moth, Synanthedon acerrubri, a pest of maples in the northeastern U.S.A., and the squash vine borer (Melittia satyriniformis) were attracted by 57.

K. (3Z,l32)-3,13-0ctadecadienylAcetate 58 (C2,H3,02) This is the main component of the sex pheromone of the smaller clearwing moth (Synanthedon tenuis). Application of Normant's carbocupration method led to a new and efficient synthesis of 58 (Scheme 165).224

8. Pheromones with a Nonconjugated Diene System

[Me(CH,)J,CuLi

> -,H C i C H Et20

L

[

I(CH,),OAc Me(CHz)~'c'c~cuLi

J'

P(OEI),

(47% overall from A)

I5

/ THF-HMPA (80%)

>

58 (99.8% pure)

Scheme 165

Szintay and co-workers synthesized 58 by Wittig chemistry (Scheme 166).225 Leznoffs polymer-support synthesis of 58 employed a 2% cross-linked styrene-divinylbenzene co-polymer containing pendant trityl chloride groups (Scheme 167).215 The synthesis of 58 and its (3E)-isomer 60, the pheromone of the lesser peachtree borer (Synanrhedon pictipes) and the peachtree borer (S. exitiosa), by the U.S.D.A. group was published as a full paper (Scheme 95, Ref. 1).226 An efficient synthesis of 58 and 60 was reported by Yamamoto et al. by an

76

The Synthesis of Insect Pheromones, 1979-1989 1) 30% H,O,HCO,H

CH,-CH(CH,),CO,H

OH

.NaN(SiMe,)pHF (50%)

H. H C:( Me(CH,),' (CH,),Br

CIHO

I

Me(CH,),P'Ph,W

OHC(CH,),CO,Me

Pb(OAc),

> HOCH,CH(CH,),CO,Me

2) NaOWMe,SO, (86%)

",

'

c:c:

Me(CH,),'

1) Ph,P/MeCN

2) NaN(SiMe,)pHF 3) OHC(CH,),OAc

'

(sox)

H

1j LIAIH,QO

(CH,),C O,Me . ..

2) PBr, (80%)

'

H, WCH,),'

c:c:

H

H,

,c:c:

(CHJe

(cH,l,o~C

58 (98% pure)

(60%)

Scheme 166

1) HO(CH,),OH C5H5N,heat

@ -TrCI 2) MsCl

> @ -TrO(CH,),OMs

LiCrCH H,N(CH,)$"z

@ -TrO(CH,),C=CH

58

Scheme 167

acetylenic route (Scheme 168).227Noteworthy is the reduction of the triple bond to @)-double bond with sodium in toluene instead of the Birch process.

L. (3E,13Z)-3,13-0ctadecadien-l-ol59 (C,8H,,0) and (3&,132)-3,13Octadecadienyl Acetate 60 (C,,H3,O2) The poplar twig clearwing moth (Parunrhrene tubuniformis) secretes 59 as its pheromone. Synthesis of 60 from commercially available (Z)-9-tetradecenyl acetate was reported by Voerman employing an acetylenic route (Scheme 169).***

8. Pheromones with a Nonconjugated Diene System

U

77

”

3) AcOH. TsOH

60 (95% pure)

(77%)

Scheme 168

60

Scheme 169 , nic chemistry inZhang et al. reported a synthesis of 59, bas d on acetvl volving the acetylene zipper reaction (Scheme 170).229 They also synthesized other three isomers in a similar fashion. HC=CCH,OH

1) LUNH,

2) WCHz)@

>

NaH

Me(CH,),C=CCH,OH

2 (

H. Me(CH,),’

c:c:

2)3

NH

2

>

(83%)

(80%)

HC=C(CH,),OH

CH

1) DHP, HCI

>-2) nBuLVdgtyrne

1) H j P - 2 Ni

Me(CH,),C&(CHz),,OTHP

H

1) TsCi/C,H,N

(CH,),OH

2) LiBr/Me,CO

H. Me(CH,),’

c:c:

2) TeOH/MeOH (92%)

“ (CH,),Br

LiC=C(CH,),OTHP

THF-HMPA (95%)

(94%)

(81%)

Scheme 170

59

>

78

The Synthesis of Insect Pheromones, 1979-1989

A mixture of 58 and 60, which attracts the cherrytree borer (Synanthedon hector), was synthesized by deconjugating the a,P-unsaturated esters A A' to the P,y-unsaturated esters B + B' (Scheme 171).230The apple clearwing

+

Me(CH,),GCH

1) n - b l i

>-2) Br(CH,),,OTHP

1) HdPbBaSO,

Me(CH,),C€C(CH,),,OTHP

2) PPTSEOH (67.5%)

(88%)

B

(58%)

B'

(57:43)

80

58

Scheiiie 171

moth (S. myopaeformis) secretes a mixture of all of the four isomers of 3,13octadecadienyl acetate (ZIE = 97/3 at C-3, and Z / E = 98/2 at C-13) as its pheromone. This mixture was synthesized by a combination of the Wittig and acetylene routes (Scheme 172).23'

a BrCH,CH(CH,),CO,H €40 I Br

CH,=CH(CH,),CO,H

KOH

HC=C(CH,),CO,H

Br

LAlH

E40

HC=-C(CH2)90H

Me(CH,),CH=CH(CH,),C=CH i)TsOWMeOHsq 2) HpaBaSO,

3)AcCVCdH5N

PCC. NsOAc CH,CI,

>

HC=C(CH,),CHO

Me(CH,),P'Ph,&' I-BuOWloluene

nbLillHF-HMPA _____) Me(CH,),CH=CH(CH,),~.C(CH,),O~HP Br(CH,),OTHP/HMPA

Me(CH,),CH-CH(CH,),CH=CH(CH2),0AC A mixlure of ell of the four isomers 01 58

Scheme 172

9. Pheromones with a Triene or Tetraene System

79

9. PHEROMONE HYDROCARBONS, ALCOHOLS, AND ACETATES WITH A TRIENE OR TETRAENE SYSTEM

A. (32,62,92)-3,6,9-Nonadecatriene61 (CI9H3J This is the pheromone component of the giant looper (Boarmia s e l e n ~ r i a ) . ~ ~ ~ It was also found as a pheromone component of the fall cankerworm moth (Alsophila p ~ r n e t a r i a )Creatonotos ,~~~ transiens, and C. gangis.234 The synthesis of 61 by Becker et al. (Scheme 173) was based on acetylenic and Wittig chemistry.232

Me(CH,),C.CH

1) E M &

’

Me(CH,),CECCH,CECH

1) ElMgBr

> -

2)

2) HCECCH~OTE

(a%)

0.

61

Scheme 173

Employing a silylated phosphorus ylide, Bestmann et al. synthesized 61 via desilylation-Wittig reaction (Schemes 174 and 175).235

61

Scheme 174

Syntheses of 61 and related methylene-interblocked Lepidopteran pheromones by acetylenic chemistry, Wittig reactions, and Kolbe electrolysis were reported by Bestmann et al. (Scheme 176).236

80

The Synthesis of Insect Pheromones, 1979-1989

(

H,

,H

P=c\CH,C&CH,CHP’Ph, Me(CH,),

I

I’

EICHO CSF

>

Scheme 176

H, ,H CEC I

Me(CHz)e

\

H, ,H CmC I

\

CH~CzCCH~

61

The pheromone bouquet of the geometrid moth (Alsophila quadripunctata) consists of (6Z,9Z)-6,9-nonadecadiene62 (C 19H36) and 61. A blend containing 61 and 62 in a ratio of 1 : 1 was most effective in attracting male moths in the field. Mangold and his co-workers prepared this blend starting from a 1 : 1 mixture of methyl linolenate and methyl linoleate (Scheme 177).237

9. Pheromones with B Triene or Tetraene System

81

B. (32,62,92)-1,3,6,9-Nonadecatetraene63 (C 19H332) This is the sex pheromone of the winter moth (Operophthera brurnat~).~~~.~~' Meinwald synthesized 6 3 by a combined acetylene-Wittig route (Scheme 178).238*240 Bestmann et al. also synthesized 63 (Scheme 179).239 PBr.jC,H,N HOCH2C&(CHz),Me

>

ErCH2C=-C(CH2),Me

(6%)

I ) BrMgC=C(CH,),OTHP

2) TsOH,MeOH

(58%)

Scheme 178

Scheme 179

C. (32,62,92,11B)-3,6,9,11-Nonadecatetraene6 4 (C,,H32) and Its (32,62,9Z,llZ)-lsomer 65 (C19H32)

These two hydrocarbons, together with 61, constitute the sex pheromone of the fall cankerworm moth (Alsophila porneraria). Wong et al. synthesized both 64 and 65 (Scheme 180).233Meinwald and his co-workers also prepared 64.241

82

The Synthesis of Insect Pheromones, 1979-1989

')

cum

H~C(CH2)ZoTHP 2) EC&CH,OTa A

> ElC=CCH,C=C(CH,),OTHP

3) HPLC puriflcation

TsoH MeOH (72% from A)

65

(Ag'-Pe&il49) (56%)

Scheme 180

D. (32,62,92)-3,6,9-1cosatriene66 (C20H36) and (32,62,92)-3,6,9Henicosatriene 67 (C,IH38) The female-produced pheromone of the velvetbean caterpillar moth (Anticarsia gemmatah) is a mixture of 66 and 67. A blend containing 66 and 67 in a ratio of 2 : 3 is most effective in attracting male moths in the field. Heath et al. prepared 66 and 67 from linolenic acid [(9Z, 12Z,15Z)-octadecatrienoicacid] by homologating the tosylate of the corresponding alcohol with either lithium diethylcuprate or lithium di-n-pr~pylcuprate.'~~ Yu and Mangold prepared a 2 : 3 mixture of 66 and 67 from methyl linolenate (Scheme 181).243

E. (32,62,92)-3,6,9-Henicosatriene68 (C2,H3*) The pheromone bouquet of the tropical pest Mocis latipes is a mixture of 68 and (6Z,9Z)-6,9-henicosadiene69 (C2,H4,,).A blend containing 68 and 69 in

9. Pheromones with a Triene or Tetraene System

83

a ratio of 3 : 1 is the most effective attractant in the field. This mixture was prepared from a 3 : 1 mixture of methyl linolenate and methyl linoleate (Scheme 182) .237

F. (32,62,92)-1,3,6,9-Henicosatetraene70 (C2,H3J The tetraene 70 is the major component of the female-produced sex pheromone of an Arctiid moth (Lrlteheisa ornatrir). Meinwald and co-workers published two different syntheses of 70.203.24' A Wittig reaction was used in the first synthesis for the construction of the terminal conjugated diene system (Scheme 183),203while in the second, that system was constructed by an elimination reaction (Scheme 184).24' Me(CH,),,C=CCH,OH

>-

PBr3

Ms(CH,),,C-CCHIBr

(62%)

(30%)

1) BrMgCeC(CH,),OTHP

2) TsOH/MeOH

70

Scheme 183 1) ElMgBr

(58%)

>

84

The Synthesis of Insect Pheromones, 1979-1989

G. (3Z,6Z,8E)-3,6,8-Dodecatrien-l-ol 71 (C,2H200) This is the trail pheromone of both the subterranean termite (Reticufirermes virginicus) and the eastern subterranean termite (R. juvipes). Yamamoto's new synthesis of 71 is based on his observation that deconjugative protonation of dienolates from (E)-2-alkenoate using potassium disilazide as the base gives (Z)-3-alkenoate predominantly (Scheme 185).245*246 CH~SiMe3 1) I-BuLflHF 1-BUS'

H

2) Tt(Oi.Pr),

{ ]="' l.BUS,$

OHC(CH,),Ot-Bu

(57%)

li(0i-Pr),

1) KN(SiMe,)pHF

M~(CH,),~CO,CH(i-Pr),

2) NH,CI aq

CO,CH(i-Pr),

Me(%)-,

LiAIH, (86%)

>

(70%)

H. (4E,6Z,lOZ)-4,6,10-Hexadecatrienyl Acetate 72 (C 18H300) and Its (6E)-Isomer 73 The cocoa pod borer (Conopomorpha crumerellu) secretes as its female-produced sex pheromone a mixture of 72, 73, their corresponding alcohols, and 1-hexadecanol. A mixture of 40 :60 :4 :6 : 10 ratio of the above five components was found to be a potent attractant. The synthesis of 72 and 73 was achieved (Scheme 186), using the appropriate sequences of acetylenic chemistry and Wittig reactions.247

I. 10,12,14-HexadecatrienylAcetate 74 (C,8H300) This is the female-produced sex pheromone of the mulberry pyralid (Glyphodes p y l o ~ l i s ) . 'Eight ~ ~ geometrical isomers of 74 were synthesized by six nonselective routes leading to a mixture of (lOZ, 12E, 14E)-74 and (lOE, 12E, 14E)-74 (Scheme 187).249The geometry of the natural pheromone has not yet been elucidated.

10. Pheromones with an Epoxy Ring

85

11UCECCH-OU

C

(70%)

-

HO(CH,),P

'Ph,Bi

>- .

0.2:89.0:1.4:9.4

1) LiN(SiMe3)2

2) Me-CHO 3) A%o/C,H,N

(CH,),OAc ..

+

(lOZ,lZE,14E).74

(lOE,lZE,i4E)-74 (33)

Scheme 187

10. PHEROMONES WITH AN EPOXY RING

A. Disparlure, (7R,SS)-(+)-7,S-Epoxy-2-rnethyloctadecane 75 (C19H380)

This is the pheromone of the gypsy moth (Lymantria dispar). (1) Syntheses of (f)-75

Four new syntheses of (f)-disparlure (75) have been published since 1979. Markgraf et al. employed Wittig olefination in the presence of 18-crown-6 followed by epoxidation to prepare (f)-75 (Scheme 188).250Brown's organobor-

86

The Synthesis of Insect Pheromones, 1979-1989

Me,CH(CH,),CH=CH,

1) H,B.SMedE$O 2) Hz02.NaOH

Me2CH(CH2)50H

CH,CI,

(7 7%)

> Me,CH(CH,),CHO

(9W

ane chemistry was used to achieve an efficient synthesis of (+)-75 (Scheme 189).25

'

Br

( 5 ~ 7 (ZWX 5 pure)

Scheme 189

Chan's synthesis of 75 is based on the stereoselective iodination of an ( E ) alkenylsilane to give a (2)-alkenyl iodide. Palladium-catalyzed coupling of the iodoalkene with an organozinc reagent yielded the desired (Z)-alkene, which was epoxidized to (+)-75(Scheme 190).99Tsuboi et al. reported a synthesis of CH,-CHCH,SiMe,

>- 1) n-BuLI.(&OK 2) Me,CH(CH,),CI

C*sMe3

Me,CH(CH,),' (78%)

MCPBA

-

O

T (f)-75

Scheme 190

h

+

[

Me,CH(CH,),CHSiMe,

I

CH=CH,

(20%)

1

10. Pheromones with an Epoxy Ring

$7

(f)-75 without recourse to 2-methyl-7-octadecene as the key-intermediate (Scheme 191)

Me(CH,),CHO

t

MeCOCCI,CO,EI

(84%)

OH Me(CH,),CHCCO,Et

I II

0 OH

M~(CH,),CHLHCH,OH

I

PI "I

NaBH,

>

ElOH (U%)

I

Me(CH2),CHCHC0,E1

I

CI

excass NaBH,

EtOH (80%)

> [ Me2CH(CH2)J2Cuti

1) NaOEVEtOH

89%

2) TsCI/C,H,N

(ea%)

(f)-75

Scheme 191

(2) Syntheses of (7R,8S)-(+)-75 Fourteen different syntheses of the bioactive (+)-enantiomer of disparlure (75) have been recorded since 1979. A . Syntheses Starting from Chiral Building Blocks. ( +)-Glyceraldehyde acetonide was employed by two groups for the synthesis of (+)-75. Lin et al. prepared all of the four stereoisomers of 75 starting from (+)-glyceraldehyde acetonide (Scheme 192).253Its treatment with decylmagnesium bromide, how-

(87%)

(7R,S)-75

Scheme 192

[a];'4 . 5 4 0 (CCI,)

88

The Synthesis of Insect Pheromones, 1979-1989

ever, yielded a considerable amount of the undesired stereoisomer. Jurczak et al. also used (+)-glyceraldehyde acetonide to prepare (+)-75 (Scheme 193).254

0

Me,CH(CH,),

2) (C0Cl)~DMSO

(63%)

fl0 OgPh+-Bu

1) W C H a ) & W

A

(M%)

o

M a i (CH,),Me

(nW,NF

CuVTHF -143". 2) M$CVC,H,N

T-0 Ph

(CH,),CHMe,

(66.6%)

THF

ow

,

(90%) (7R,BS)-75

Scheme 193

[alo.to.eo (CCIJ

In their case, the Grignard product was first oxidized to a ketone A, which was reduced with L-selectride@to give the desired isomer B after silylation in more favorable selectivity of 9 : 1 . Masaki et al. synthesized (+)-75 starting from (+)-tartaric acid (Scheme 194).255They utilized a cleavage reaction of an intramolecular acetal A with an organoaluminurn reagent to give B.

10. Pheromones with an Epoxy Ring

-

89

Achmatowicz et al. achieved a synthesis of (+)- and (-)-75 from o-glucose (Scheme 195).256Two out of the four chiral centers of D-glucose were utilized, CHO

Me,CH(CH,),PPh,Br

1) H p d - C

NaWDMSO

2) NaH. PhCH,CI

Of-

(47%)

DMSO (71%)

dtl CF,CO,H

ok

A

(62%)

OH

C,H, (6296)

(-"lWh)

1) A%O/C,H,N

(87%)

3) TsCI/C,H,N

(76%)

(+75

[a]:' +o.~O(cci,)

(4.75

[ajOp-O.~O(CCI,)

1) TsCVC,H,N (84%)

(65%)

Scheme 195

and the unwanted two chiral centers were removed by the glycol cleavage reaction (A + B). D-Ribose served as the starting material in Wightman's synthesis of the lactone A (Scheme 196),257which was the key intermediate in Marumo's synthesis of (+)-75.258

Scheme 196

90

The Synthesis of Insect Pheromones, 1979-1989

A synthesis of (+)-75 was reported by Tolstikov et al., which consists in the conversion of D-galactinal triacetate to (2R,3S)-2,3-epoxy- 1-tridecanol (A in Scheme 197).259 (-)dehylm

‘p’

1 9

Ti(Ci-Pr), , t-BuOOH CH1C12, 4 0 OC, 4 days

CrO, .2CsHSN

>

CH,CI, (88%)

H+@

(80%)

A (0lre.e.)

B. Syntheses Based on Chemical Asymmetric Reactions. Four papers have appeared reporting the application of the Sharpless asymmetric epoxidation to disparlure synthesis. Sharpless et al. converted the epoxy alcohol A (Scheme 197) to the corresponding aldehyde B, to which the remaining carbon chain was attached by a Wittig reaction ,260 Mori and Ebata prepared optically pure (+)-75 as shown in Scheme 198.261,262 Optically impure epoxy alcohol A, which was prepared by asym-

koH

(+)-diethy1 tanrate Ti(O+Pr),, I-BUOOH

1) Par3/ ESO

2) LiCsCCH,OLi THF-NH~

(92%)

C H Z C I ~-23’C. , 46 h

(83%)

(46%)

0

NO2 1) &COS/ MeOH

Recrysl‘n

2) TsCI / C,H,N

3

mp 81-82%

(65%)

A (84Sbe.e.)

B

[Me(CH,),),CuLi El,C-toluene

I

(69%) (t)- 75

[u]D”t0.60(CC14)

Scheme 198

(84%)

O H % H*

(loo%le.)

10. Pheromones with an Epoxy Ring

91

metric epoxidation, was purified by recrystallizing the corresponding 3,5-dinitrobenzoate R to give, after hydrolysis, optically pure A. The corresponding epoxy tosylate was treated with lithium di(n-nony1)cuprate to give ( +)-disparlure 75. Wicha and his co-workers developed a new method for the preparation of allylic alcohols from alkyl phenyl sulfone and trimethylsilylethylene oxide, and used it for the synthesis of Mori's epoxy alcohol (Scheme 199).263A full report of this work appeared recently. Io9' 1)n.BuLi

Y"" /

2) & , s i p

1) PhSH, AIBN. 80°C. 4h

Z)H,O,/AcOH (95%)

7

z

P

T

h

O

H

E:Z= 1:13

A

1) (+)dielhyl tanrate

Ti(Oi-Pr)q.I-BuWH

0,"

(4-75

(30% lrom A)

Scheme 199

Lin et al. prepared an epoxy alcohol A through the kinetic resolution of (k)1-tridecen-3-01 by Sharplress asymmetric epoxidation (Scheme 200).*@'(+)Disparlure (75) was synthesized from A in five steps in 60% overall yield. OH \

\)vvvvv

h-(+)dieW~yl tamale Ti(0i.Pr)4

'

t-BuOOH/CH,CI, -

OH

CH,CI,

0

-26-3ooC. b7days (56% or 20%)

Scheme 200

DHP. PPTS

A (9PAe.e.)

(89%)

92

The Synthesis of Insect Pheromones, 1979-1989

Kametani et al. achieved a formal synthesis of (-t)-75 from an oDticallv . . active 2-furylcarbinol prepared by the kinetic resolution according to Sharpless. 1227. 1228 Alkylation of an optically active sulfoxide was used in Yamakawa’s synthesis of (+)-75 (Scheme 201).2659266 Alkylation of A with decyl iodide to give B

(75%)

B

A

was followed by aldol reaction of B with 6-methylheptanal to give a separable mixture of C and D. The former gave (+)-75, while the latter gave (-)-transisomer of 75.

C. Syntheses Based on Biochemical Asymmetric Reactions. Tsuboi et al. prepared the epoxy alcohol C, which was used by Sharpless as the key-intermediate leading to (+)-75, employing the yeast reduction (Scheme 202).267Re-

A

syn-B

48

C ( >95%e.e.)

Scheme 202

.

52

anti-8 ( 295Vae.e.)

( r95%ee.)

10. Pheromones with an Epoxy Ring

93

duction of an a-keto ester A yielded a separable mixture.of hydroxy esters, synand anti-B. Further transformation of syn-B yielded the epoxy alcohol c. Bianchi et al. used porcine pancreatic lipase (PPL) for the asymmetric hydrolysis of (*)-A (Scheme 203)268to yield (2S,3R)-B, which was an interme-

PPL, pH 7.6 25OC. 1.5h

>

0:. H

(2R,3S) - (-). C

OAc

(2S.3R) - D

(>95%e.e.)

Scheme 203

diate in Mori's synthesis of ( +)-75.262Similarly, asymmetric transesterification of ( f ) - C with ethyl acetate in the presence of PPL yielded (2R,3S)-C, the Sharpless intermediate. Otto et al. treated (*)-epoxy acid A with Pseudomunus NRRL-B-2994 and obtained (9S, 10R)-A. Kolbe electrolysis of this with n-butyric acid gave (+)-75 (Scheme 204).269

Scheme 204

Over a decade ago, Iriuchijima reduced ( f)-phenylsulfinylacetone A with baker's yeast to give in 28% y.ield optically pure (S)-A.270Starting from @)-A,

94

The Synthesis of Insect Pheromones, 1979-1989

Fujisawa and his co-workers accomplished the synthesis of (+)- and (-)-75, demonstrating the utility of the chiral sulfoxide A (Scheme 205).271

(47%)

(72%)

1

(46%)

3) NaOH (46% overdl yield from C)

Scheme 205

B. (6Z,9S,10R)-9,10-Epoxy-6-henicosene 76 (C21H,,O) This is a pheromone component of the ruby tiger moth (Phragmatobiafuliginosa). A synthesis of (*)-76 by Bell and Clacclo employed alkylation of tosyloxy epoxide A to give C (Scheme 206).272 D-Xylose was converted to (9S,10R)-76 by Rollin and Pougny (Scheme 207).273Their product, however, was contaminated with 10%of its (E)-isomer. Another synthesis of both the enantiomers of 76 was recently achieved by Ebata and Mori (Scheme 208).274Two chiral centers of 76 were introduced by Sharpless epoxidation to give B from A. Recrystallization of B gave pure B

10. Pheromones with an Epoxy Ring

\

95

(50% lrom A) C

Scheme 206

with > 99% e.e. Normant's carbocupration method was used for the chainelongation of the tosylate C to give 76. This process was quite efficient to give 76 in five steps from propargyl alcohol in 14% overall yield. C. (32,62,9S,10R)-9,1O-Epoxy-3,6-henicosadiene 77 ( C , ,H,,O) This is a pheromone component of the salt marsh caterpillar moth (Estigmene acrea), the fall webworm moth (Hyphanfria cunea), and two Asian moths (Creatonotos transiens and C. gangis).

A

em-•

Scheme 208

(9R.10!3)-76

[a," -9.1°(CHCl,)

10. Pheromones with an Epoxy Ring

97

Nikolaeva and Kovalev reported a synthesis of (*)-77 (Scheme 209).275 ELCsCCH,C=CMgBr

H.

,c = c;

+ CICH,

H

MCPBA

(CH,)ioMe

H,

0

P-2Ni

Scheme 209

(f)-

Another synthesis of (f)-77 was reported by Bell and Clacclo by the same method as used for the synthesis of (f)-76 (Scheme 210).272

A

(+).77

Scheme 210

Mori and Ebata synthesized both the enantiomers of 77 employing the Sharpless asymmetric epoxidation (Scheme 21 1).26'*262 Epoxidation of trienol A in JBr

I)ErMgCrCCH,OMgEr

CUCI/THF

2) PEroI E$0.C6H5N

,

ErMgC=CCH,OEE CuClITHF (62%)

98

The Synthesis of Insect Pheromones, 1979-1989

the presence of (-)-diethy1 tartrate gave (2R,3S)-B, while the use of (+)-diethy1 tartrate afforded (2S,3R)-B. Purification of B was achieved by recrystallization of C to give optically pure B, the tosylate of which was treated with lithium didecylcuprate to furnish (9S,10R)-( +)-77.Similarly, (-)-77was also synthesized. Only (9S, 10R)-77was bioactive when tested by EAG. Pougny and Rollin reported a synthesis of (+)-77starting from D-xylose (Scheme 212)276in a manner similar to their synthesis of 76 (Scheme 207).273

-

t i o H S O H 5sleps OH D.xybse

1 ) V P P h , / T H F ,

Z)MsCl/EL,N (64%)

M

s

ox

T

1) TsOH / MeOH (75%)

A synthesis of related chiral bis-homoallylic epoxides was achieved employing asymmetric e p o x i d a t i ~ n . * ~ ~

D. (3Z,6Z,9S,10R)-9,10-Epoxy-1,3,6-icosatriene 78 (C20H340)and (3Z,6Z,9S,10R)-9,10-Epoxy-1,3,6-henicosatriene 79 ( C ,,H,,O) These are the pheromone components of the fall webworm moth (Hyphantria cunea). A mixture of (3Z,6Z,9S, 10R)-77, (92,12Z)-9,12-octadecadienal, (9Z, 12Z,15Z)-9,12,15-octadecatrienal,78,and 79 attracted male fall webworm moths into traps. Both thc cnantiomers of 78 and 79 were synthesized employing the Sharpless asymmetric epoxidation in the manner similar to the synthesis of 77 (Scheme

2 1 3 ) . 2 7 a . 279

11. CHIRAL ALCOHOLS AND THEIR ESTERS AS PHEROMONES Many chiral alcohols and their esters serve as insect pheromones. In this section, individual pheromones are arranged in increasing order of the length of the main carbon-chain of alcohols or the alcohol part of esters. Use of organ-

11. Chiral Alcohols and Their Esters as Pheromones

T

T

H

H

p

o

P

~

o

,

H2/ Lindar-Pd quinoline , / AcOEl (71% horn A)

'

Br I ) KOH/ MeOH-EOH O ~ 2)PPTSIMeOH (55%)

'

H O -

THPO

- -

-

OH

1) MsCI/EL,N Z)LiD/THF

99

>

(87%)

-

E

-

(-)diethy1 lartrate Ti(0i.Prj4, bEu00H, Ms 4A / CH,C12 (60%)

'

(9S,lOR)-78 (mp 14-15'C) lalo's 4 . 4 1 ' (CHCI,)

Similarly

(t)-dielhyllarlrale Ti(Oi.Pr),. I-BuOOH, MS 4A / CH,CI,

' Scheme 213

oboranes in enantioselective viewed. 280-282

(QR,lOS)-79

lalo" t0.62'

(CHCI,)

syntheses of alcohols was recently

re-

A. Dominicalure 1 [(S)-1-Methylbutyl (E)-2-Methyl-2-pentenoate] 80 (Cl IH2002) and Dominicalure 2 [(S)-1-Methylbutyl (E)-2,4Dimethyl-2-pentenoate] 81 (C 12H2202) Dominicalure 1 (80) and 2 (81) are the male-produced aggregation pheromones of the lesser grain borer (Rhyzopertha dominica). They are attractive to both sexes of that insect.

The Synthesis of Insect Pheromones, 1979-1989

100

The racemates and the enantiomers of 80 and 81 were synthesized (Scheme 214).283The enantiomers of 2-pentanol were prepared from the enantiomers of

(51%) 75

~

25

(79%)

92 : 8

NH2

HNO,

>

H0,C4C02H

ccy

(70%)

Q‘

1)H3B’SMez

2) TsCl/ CSHSN

3) Lil / Me,CO 0

(S)-(+)-Glutamicacid

(k).80

LiAIH,

THF (70%)

(known)

HO-

OH

i)TsCI/C,H,N

2) LiAIH, / THF (28%j

2 3

(S)-2-Penlanol

[a]? + i 3 . I 0 (EIOH)

’

OH

(R).(-).Glutamic add

M

-,”?’

(R)-P.Penlanol (a],25-13.20 (EIOH)

; (S)-80 (a]025 +31.5’ (EGO) Natural: +32.i0

3

$ o j (S)-81 [a],25 +32.0° (EGO) Natural: +32.3’

Scheme 214

glutamic acid. The natural 80 and 81 were shown to be enantiomerically pure (+)-isomers, as revealed by the [aIDmeasurement and NMR study. The natural (S)-(+)-80 and 81 were about twice as active as the unnatural ( R ) - (-)-80 and 81 as assayed by their field test. Moiseenkov and his co-workers also synthesized ( f ) - 8 0 and (*)-81 (Scheme 2 15).284

11. Chiral Alcohols and Their Esters as Pheromones

101

B. (R)-1-Methylbutyl Decanoate 82 (C 15HJ002) This is the pheromone of the bagworm moth (7'hyridopteryx ephemeraeformi^).^^' Both (R)-82 and (S)-82 were synthesized and bioassayed (Scheme 216).285Only (R)-82 was active. The (S)-enantiomer was inactive without any inhibitory effect against (R)-82.

(R) . 8 2

Scheme 216

C. (3R,4S)-4-Methyl-3-hexanol 83 (C7H,hO) Pasteels et al. identified 83 as a pheromone by extracting the heads of all adult castes of the ant (Tetramorium impurum).2x6 Kato and Mori synthesized 83 starting from methyl (R)-3-hydroxypentanoate (Scheme 2 17).287Because of the unsatisfactory enantiomeric purity (92 76 e.e.)

pure 13

A (9w'e.e) anti. syn = 92.8

&co,Me HO

1) DHP, PPTS

z)LIAIH,

,

3) TsCl I CsHSN (91%)

o T ~ -.!,,,

1lMe,Cu~IEp OTHP

2) TsOH I MeOH

(51%)

HO (3R.4S) - 83

A (IW%e B )

Scheme 217

of the starting material, the intermediate A was purified as its 3,5-dinitrobenzoate B to make it both diastereomerically and enantiomerically pure.

D. (3S,4S)-4-Methyl-3-heptanol 84 (C8HI!@) This is a component of the aggregation pheromone of the smaller European elm bark beetle (Scolytus rnultistriatus). 288-289 Recently, its (3R,4S)-isomer was identified as the trail pheromone of the ant (Leprogenys diminuru).290

102

The Synthesis of Insect Pheromones, 1979-1989

( I ) Syntheses of (rt)-84 Three syntheses of (3R*,4R*)-(+)-84 were reported. Schlosser and Fujita synthesized (+)-84 by the addition of dimethyl (Z)-2-butenylboronate to propanal, followed by the transfer of a methyl group of trimethylaluminum to the double bond in the presence of titanium tetrachloride (Scheme 21 8).2y'

OH

OH 96

TiCI, / THF 00- 1 MOC (32%)

: 4

OH

OH

(*)

-84

Scheme 218

Koreeda and Tanaka employed the Lewis acid-catalyzed addition of tri-nbutyl- I-methyl-2-butenyltin to propanal for the synthesis of (f)-84 (Scheme 2 1 9).292

(nBu),Snli/THF C

-78%. 4h

>

B F i OEb/CH,CI,

(n-Bu),Sn

-78'C, 10 h

(95%)

-+

(80%)

i

H,/Pd-C EIOH

OH

(93%)

OH

Scheme 219

Kallmerten and Gould prepared ( +)-84 by the enolate Claisen rearrangement of 0-benzylated 1 -methyl-(E)-2-butenyl glycolate to give an acyclic product with syn-stereochemistry (Scheme 220).2'3 Optical resolution of (+)-84 was reported by Blight et al.2'4

11. Chiral Alcohols and Their Esters as Pheromones

103

0 kOCH,Ph

1) n-BuU

1) LDA/THF, -78'C

2) TMSCI 3)MeOH 4) CH$J,

'

C02Me

LiAiH4

>

2) MsCl

OH

OCH,Ph

OCH2Ph

3)Me2CuLi

'

(44%)

H, I Pd-C MeOH

OCH,Ph

OH

(f).04 Scheme 220

(2) Syntheses of Optically Active 84 Starting from Chiral Building Blocks Mori and Iwasawa's first success in synthesizing the natural (3S,4S)-84 in 1980 was based on the enzymatic resolution of (f)-rhreo-2-acetarnino-3-methylhexanoic acid A (Scheme 221).*05The amino acid ( 2 R , 3 S ) - B was converted to epoxide C, which was treated with lithium dimethylcuprate to give (3S,4S)-84.

i

-OH

2)NaOMe/MeOH (47%)

Similarly

(2S.WB

f

1) HBr-AcOH OH

Me,CULi

q0

C

EbO (75%)

'

OH (35,4S)-84

[alDn-21.7'

=?, (3R,lR)-84

[ulDn",227'

Scheme 221

(hexane)

(hexane)

104

The Synthesis of Insect Pheromones, 1979-1989

Pougny and Sinay synthesized, in 35% overall yield, the natural and bioactive (3S,4S)-84 starting from D-glucose (Scheme 222) .296

-78%

HO

6

OH

OH

OH

HCI

OH

>

',"?

oHcA3 1)MeCH=PPh3

IoIu8ne

2) PhCH,Br I DMF BaO. 8alOH),

-4OOC

>

(3S.45).84

Scheme 222

A synthesis of (-)-84 from (+)-3,7-dimethyl- 1,6-0ctadiene was reported by Serebryakov and his co-workers (Scheme 223).297

(61%)

O

w

0

x

> (79%)

@o

x

1) AczO / CH ,N , 2)AcOH (73%)

Ho

Scheme 223

(3R,4S). 84

11. Chiral Alcohols and Their Esters as Pheromones

105

(3) Syntheses of Optically Active 84 by Asymmetric Reactions In Frater's synthesis of (3R,4R)-84, partially enantioselective reduction of ethyl 3-oxopentanoate to (R)-A with baker's yeast was followed by its diastereoselective alkylation to produce B, which eventually furnished (3R,4R)-84of 40% e.e. (Scheme 224).2y8 0

&C02El

HO

OTHP

baker's yeas1 2) DHP/ PPTS

(67%)

(58%)

A

1) LiAlH, / EGO

2) TsCl I C,H,N (89%)

'&

l)PhSH.l$C03>

diiH2S04

(72 5%)

2)Li/EtNH2

CH20T6

(56%)

(3R.4R). 84 40%e.e

Scheme 224

Vigneron et al. synthesized pure (3S,4S)-84 by employing their asymmetric reduction of acetylenic ketones (Scheme 225).2yy,3mTheir asymmetric reduction of A afforded B (80% e.e.). The acid C prepared from B could be recrystallized to give C of high e.e., which afforded unsaturated iactone E with

1) n-BuLi / THF

E'pco, 2)

El

0

H OH

B

A

1) Me,CuLi

Me. El . ' G O H

Ph,P=CH, (64% from F)

>

>

(8Phe.e.)

"'bo

Me El

(60.80% lrom A )

l ) H /Raney-Ni

H, I Raney-Ni

6H

MeOK

Me Et "

"

~

> +

0

(i-Bu)plH

6H

(35.45)-84

[alD25 t23' (hexane)

Scheme 225

>

106

The Synthesis of Insect Pheromones, 1979-1989

>98% e.e.300 Its hydrogenation was fairly selective to give the cis-lactone F as the major product. The lactone F was further manipulated to give (3S,4S)-84. Matteson's enantioselective synthesis via pinanediol boronic esters yielded (3S,4S)-84 of high e.e. (Scheme 226).30'*302

Nakagawa and Mori synthesized (3S,4S)-84 employing asymmetric epoxidation coupled with regioselective cleavage of the epoxy ring with trimethylaluminum (Scheme 227).303

(84% me.)

Scheme 227

Shimizu and co-workers prepared (3S,4S)-84 (92% e.e.) by means of the Sharpless epoxidation and palladium-catalyzed selective hydrogenolysis of the derived alkenyl epoxide with formic acid (Scheme 228).3u Hoffmann et al. reduced cyclic P-keto ester A (Scheme 229) to give hydroxy ester B (83% e.e.), which was purified by recrystallizing the amine salt of the corresponding acid C.305 Starting from the pure ester B, (3S,4S)-84 was synthesized. Nakai and co-workers employed asymmetric [2.3]-Wittig rearrangement for the synthesis of (3S,4S)-84 (Scheme 230).306The starting alkynol was obtained by optical resolution.

11. Chiral Alcohols and Their Esters as Pheromones 0

I)(+)-dielhyllartrale

I1

-

Ti(Oi.Pr)4, I-BuOOH

(EIO),PC-HCO,Me

2)(COCl),, DMSO, ESN/CH,CI,

CHCI,

Pd,(dba):

A HCO,H, (n-Bu)3P

&C02Me0

(63%)

>

1)DHP. TsOH

4 - 0OH 2 ”

3)TsCVC,H,N

E Y (91%)

(41%)

1)LAHfWF OTHP

2)3N HCI

OH

(38,4S).84

(31%)

*dba=dibenryii&ne amlone

lul,n-19.40(hexane)

Scheme 228

b c o 2 ~ baker’s . yeas1 (71%) A

OH (J,CO~M~

B

KOH

aq t.+sf3H

(83% e.e.)

0 OH

(96%)

YH2 1) (S)-PhCHMe

COzH 2)Recrysln.

C

A 3)H30’

4)MeOH. H’ (72%)

(a]Dm-19.60(hexane) (S,4S):(3S. 4R)=93:7

Scheme 229

76 HdRaney-Ni

OH

6H (38.45)-84 (98% e m ) [a]D’8-21.40(hexane)

Scheme 230

107

108

The Synthesis of Insect Pheromones, 1979-1989

Fujisawa et al. prepared (3S,4S)-84 employing chirality transfer in the ester enolate Claisen rearrangement of (2E, 1R ) - 1-methyl-2-butenyl glycolate as the key-step (Scheme 231)."07

4)NaOHIMeOH

(35. 45)-84 (83% e.e.) (a],n-18.80(hexane)

Scheme 231

Oppolzer and Dudfield employed asymmetric cr-acetoxylation of a carboxylic ester for the preparation of glycol A (Scheme 232),'08 which was the keyintermediate in several other syntheses of (3S,4S)-84.

E. 3-Octanol85 (C8H,80) The mandibular glands of Myrmica ants contain 3-octanol 85. Myrmica scabrinodis and M . rubra were attracted by (R)-85.'" In the case of M . scabrinodis, the naturally occurring mixture of (R)-85 and (S)-85 (9 : 1) is more active than (R)-8Sa309Other ants like Crematogaster castanea and C. liengmei seem to use (S)-85 as their p h e r ~ m o n e . ~ ' ' Pure enantiomers of 85 were synthesized from pure enantiomers of methyl 3-hydroxypentanoate (Scheme 233) by conventional chain-elongation." I

--

11. Chiral Alcohols and Their Esters as Pheromones

LcozMe A 2)LiAIH

OTHP

3)TsCWC,H,N

(-1009~ e.e.)

OH

A

T

U,CUCI,

s

(57%)

(Fib85 [U],~-~.~~(CHCI,)

OH

> -

&CO,Me

O

109

+

(51-85 [~]~~+10.1~(CHCl~)

Scheme 233

F. (2S,3S)-2,3-0ctanediol 86 (C,HI,O2) The grape borer (Xylotrechus pyrrhoderus) is a major pest of grapevines in Japan. The male-produced sex pheromone is a mixture of (2S,3S)-2,3-octanediol 86 and (S)-2-hydroxy-3-octanone 137 in a ratio of 80: 20-95 : 5. Sakai et al. prepared both the enantiomers of 86 from tartaric acid (Scheme 234; details of the synthesis are not reported)."' OH

__3

H02ChCo2H 6H (-)-Tanarb acid

6H (2s. 3S)-86 [a]~'-19.2°(CHC1J

Scheme 234

Mori and Otsuka synthesized (2S,3S)-86 from ( +)- 1-octen-3-01 employing the Sharpless asymmetric epoxidation as the initial step (Scheme 235).313The overall yield of (2S,3S)-86 from (*)-A was 19% in six steps.

KOH

0,,

+aqMeOH (79%)

~ E E

6H

(ZS,

(W%)

2)HClOJaq THF

6H

(74Y0)

(25. 351-86 [a]D2'-18.50(CHCI,)

(92% e.e.)

Scheme 235

110

The Synthesis of Insect Pheromones, 1979-1989

Masaki's synthesis of (2S,3S)-86 utilized (+)-tartaric acid as the starting material (Scheme 236).255By the route which had been employed in their syn-

(71%)

Raney-Ni EOH (70%)

OH OH (2S,35)-86 lal~'-15.B0(CHCI,)

Scheme 236

thesis of (+)-em-brevicomin, (+)-dimethyl tartrate A and the sulfone B were converted to C. Cleavage of the bicyclic acetal C to yield D was followed by further transformation to generate (2S,3S)-86. Servi and his co-workers also prepared (2S,3S)-86 (Scheme 237)."' The starting material A was prepared by employing baker's yeast in the key-reduction

(59% overall)

A

(25, s)-88

Scheme 237

--

Veschambre reduced 2,3-octanedione with a fungus, Beauveria sulfirescens, to give (2S,3S)-86 (Scheme 238)."'

6y4F

OH

0

6H

(70%)

(45%)

(2S, 3S)-BS

(aj~5-160(CHC13) (99% e.e.)

Scheme 238

11. Chiral Alcohols and Their Esters as Pheromones

111

G. (R)4-Methyl-l-nonanol 87 (C,,H,,O) This is the sex pheromone of the yellow mealworm (Tenebrio moliror). By synthesizing both the enantiomers of 87 from (R)-citronellol, Tanaka et al. determined the absolute configuration of the natural 87 as R (Scheme 239)."' l)Mg/E$O

l)TsCI/C5H,N

H o A C O z M e

p)EhcuL'

-

C

0

,

(35%)

WCH,),MgBr

U

O

T

s

U,CuCI,~HF

UAIH,

A

M

e

EhO (65%)

(R)-87

[aIoa+1.33'(CHCI3)

h

(66%)

(47%)

HIO4.2H,O ,

;

d

(76%)

O

H

C

L

(71%)

L

O (S)-87 [a)Dp-l.320(CHC13)

H

Scheme 239

Their synthetic (R)-87 was as active as the natural 87. (S)-87 did not show any synergistic or antagonistic activity. Carpita et al. synthesized (*)-87 and the two enantiomers of 87 (Scheme 240) . 3 1 8

H. (R)-Nostrenol [(2)-6-Undecen-2-01] 88 (C I ,H,,O) This is the volatile signal of ant-lions (Euroleon nostrus and Grocus bore). Baeckstrom et al. synthesized (*)-88 and the two enantiomers of 88 (Scheme 241).3'9 The natural compound was shown to be enantiomerically pure (R)-88 ( > 99.9% e.e.).3'9

The Synthesis of Insect Pheromones, 1979-1989

112

A

c

o

,

M

e

OH

>' (21% overall)

(R)-87

,

l)$+.i-ci

_j

imidazolelDMF

4-

HO 2)LMIH,/E$O

(24% overall)

3)TsCI/C,H,N 4)[Me(CH,),12CuLi/E~0 5)H30'

Scheme 240

OH

Me(CH,),CH=PPh,

PCC OH

(93.99%)

2:E-zlO:l

(708WO)

ESO. -80°C (72%)

cfw

(88%)

PhC0,H. Ph,P EO,CN=NCO,EI (78%)

Scheme 241

OH (S).87

CH,CI, (87%)

11. Chiral Alcohols and Their Esters as Pheromones

113

I. 1,7-Dimethylnonyl Propanoate 89 (C14H2802) Guss et al. isolated 10 pg of the female-produced sex pheromone of the western corn rootworm (Diubroficu virgifera virgifera) and identified it as 1,7-dimethylnonyl propanoate 89.320A diastereomeric mixture of all of the four isomers of 89 was synthesized (Scheme 242) and shown to be attractive against

Scheme 242

the males of the western corn rootworm."' It was also attractive against D. virgifera zeae, Mexican corn rootworm ( D . longicornis), D. porrucea, and northern corn rootworm (D.barberi)."' All of the four possible stereoisomers of 89 was prepared by Sonnet et al. via optical resolution of the intermediates.'*' They first synthesized (lR,7RS)-89 and (1S,7RS)-89 (Scheme 243).32' This synthesis involved the HPLC separaMe

A>

OH

'1 UCECCHOTHP

L

B

Hdp'.c>

r AcOH

(80%)

&Br

2)H,O'

/ /

(83%)

2)HPLC separation

(1R. 7AS).8B OCOEt

4)KOH/MeOH

(IS.7RS)-8B

Scheme 243

114

The Synthesis of Insect Pheromones, 1979-1989

tion of the diastereomers employing (R)-a-methoxy-a-trifluoromethylphenylacetic acid (MTPA) as the derivatizing agent. Subsequently, they synthesized all of the four isomers by HPLC separation of the intermediates (Scheme 244).322For the preparation of (lS,7S)-89 and (IR,7S)-89, commercially avail-

-

1)HPLCsepn.

l)NsBH,

OCN& OCN

‘) ‘)

\

O & H ,

+

(IS.7R)-89

[a)T-3.77°(CHCI,)

3)(EICO),O

ti

6

I-+G OCOEI

1

(lR, 7R)-89 [~]~-7.87~(CHCl,)

\

SOCI,

d Bu,N

1)MflHF P)LiBr,CuBr

0 0

-ci

1)dil H2S04

2)NaBH,

3)

,

3)

(boo4

(qua4 1)HPLC sepn. OCOEI

(IS,75)89

(a],2St8.600(CHCI,)

OCOEI

(1R, 751.89 [U)~~+~.~~~(CHCI,)

Scheme 244

able (S)-2-methyl- 1-butanol (99.2-99.5 5% e.e.) was employed as a starting material, while for the synthesis of (1S,7R)-89 and (lR,7R)-89, D-isoleucine was employed. The key-step was the HPLC separation of the diastereomeric carbamates B derived from the corresponding alcohols and (R)-1-( 1-naphthyl)ethyl isocyanate. Biotests of the four synthetic isomers of 89 revealed the following stereochemistry-bioactivity reIati~nships.”~-”~ Males of D. virgiferu virgiferu and D. virgiferu zeae responded strongly to the (1R,7R)-isomer and secondarily to (lS,7R)-89, while D. porruceu responded exclusively to (lS,7R)-89. The (1S,7S)- and (lR,7S)-isomers were inactive in all tests. Synergism or inhibition

11. Chiral Alcohols and Their Esters as Pheromones

115

was not detected when mixtures of isomers were tested against D. virgifera virgifer~.~*' Only the (lR,7R)-isomer was attractive to the northern corn rootworm (D. b ~ r b e r i ) . Inhibition ~*~ of D. barberi response to (1R,7R)-89 took place when either the (1S,7R)- or (1S,7S)-isomers were in the testing sample. (1S,7S)-89 was inactive against D. barberi. Thus, the propanoates attractive to rootworm species were (lR,7R)-89 and (lS,7R)-89. Mori and Watanabe accomplished the enantioselective synthesis of bioactive (1R,7R)-89 and (1S,7R)-89, starting from chiral building blocks as shown in Scheme 245.325Building block (R)-Awas prepared from enantiomerically pure

0

1)bakets yeast

K/C02E1

2)punfication

(36%)

-

,

OH

&C02E1

+

OTHP

__j

(SW

( 100% 8.8. )

1)Aaney Ni 2)AcOH, aq THF

3)EcOCVC6H5N (38%)

(RpA

t

D

( t ~7 , ~ ) 4 ~ [alDan-7.57O(c~c~~

+

(S)C

OCOEt

++-P 3 3

[a~02'-4.250(CHCl,)

Scheme 245

(R)-citronellol, while the enantiomers of another building block C was derived from the pure enantiomers of ethyl 3-hydroxybutanoate B. Connection of A with B employing D as the pivot generated the carbon framework of 89, which finally yielded (1R,7R)-89 and (lS,7R)-89.

116

The Synthesis of Insect Pheromones, 1979-1989

By employing Mucor miehei lipase as the resolving agent, (lR,7RS)-89 and (1S,7RS)-89 were prepared by Sonnet and Baillargeon (Scheme 246).”‘

-

0

Mucor rniehei lipase pH 7.0, 24h

(2540% conversion)

OAc t

4.51 g

Me(CH,),CO,H 0.43 g

-__ M. rniehei lipase

>-

30%. 6 weeks

(IR. 7RS)-BB 0.67 g (97.6%e.e.)

&

i

Residue

1.83a (94 6% e.e.)

0

(93.2%e.e.)

Scheme 246

A synthesis of (1RS,7R)-89 was achieved starting from (S)-( +)-3,7-dimethyl-l,6-octadiene.”’

J. Lardolure [(lR,3R,5R,7R)-1,3,5,7-Tetramethyldecyl Formate] 90 (C15H3002)

Lardolure 90 was isolated by Y . Kuwahara et al. as the aggregation pheromone of the acarid mite (furdoglyphus konoi). This mite is a primary pest for stored products such as dried meat and fresh meal. Y. Kuwahara et al. identified the pheromone as 1,3,5,7-tetramethyldecylformate (90) by synthesizing its diastereomeric mixture, which was found to be bioactive. Their synthetic route is shown in Scheme 247.”’ The synthetic mixture consisting of the eight diastereomers of 90 showed seven peaks when analyzed by capillary GLC, and the peak exhibiting the shortest retention time coincided with that of the natural 90. Y.Kuwahara et al. assigned (R)-configuration to C- 1 of the natural 90 by comparing both the NMR spectral and chiroptical properties of the natural 90 with (S)-1-methylheptyl formate.”’ In order to establish the stereochemistry of 90, Mori and S . Kuwahara carried out three different syntheses of 90 (Scheme 248).329By these routes, 1,3-syn-90, 1,3,5-syn-90, and 5,7-syn-90 were prepared and analyzed by capillary GLC to reveal the fact that all of them exhibited the peak due to the natural 90. The natural pheromone was therefore thought to have a 1R,3R,5R,7R configuration.

-

1)TsCI/C,H,N

1)MeOH. H2S04

~

Z)TsCVC,H,N

s

o

~

~

~

(82% hom 8)

B

-&OH 2

-

&

2)Nal/Me2C0

(93%)

1)I-BUfiIH

2)N,H,. KOH

THF (50%)

Scheme 248

3)HC02H (61%)

U

O

C

H

O

(1R'S'. 3R'S', 5R', 7R')-W

117

The Synthesis of Insect Pheromones, 1979-1989

118

Mori and S. Kuwahara then accomplished the synthesis of (lR,3R,SR,7R)-90 and its antipode (Scheme 249).330Optical resolution of the lactone A yielded

(91%)

8 (mixlure)

A

l)K&O.jMeOH

2)dil HCI (33% from 8)

2)dil HCI (27% hcm 8)

H02CU

(+).I?

O

2)PDC

I-kE

H

2)NaOH 3)TsOH

W=

l)MOMCl.(i-Pr),NEWCH2Cl2

OH

2)UAiH4

OH

&CO,Me l)TsCVC,H,N

HoyvJIoMoM 2)NaVAn.DMF) (9% horn (t)-E)

(-10

(7QW

I

(IS,3S,59,75)-90 [alDnt3.60(hexme)

Scheme 249

(+)-E and (-)-E. The absolute configuration of (-)-E as depicted in Scheme 249 was proved by its conversion to the known (--)-F. The key building block ( - ) - G was prepared from (+)-E. Alkylation of methyl (S)-3-hydroxypentanoate (H) with (-1-G gave the anti-alkylation product I, which was converted to (lR,3R,SR,7R)-90. Similarly, (-)-E and (R)-H furnished (lS,3S,5S,7S)-90. Only (IR,3R,SR,7R)-90 was attractive against the mite.

11. Chiral Alcohols and Their Esters as Pheromones

119

K. 10-Methyldodecyl Acetate 91 (ClsH3,0z) This is a minor component of the pheromone bouquet of the smaller tea tortrix moth (Adoxophyes species) . 3 3 (R)-91 was found to be slightly more bioactive than (S)-91.333Further field tests suggested that there is an optimum R : S ratio of 95 : 5 for trapping of A synthesis of (&)-91was reported by Sonnet and Heath (Scheme 250)?

- 1)2LDILrlHF-HMPA

HozC(CHz)~CHmCHz

2)ElBr

(74%)

OH

1)Ph,Pd3r.p2H,Clz

(CH,),CH-CH,

2)LiEqBH

d'

3)HzOz. NaOH

COZH (CHz),GH-CHz

WH,/THF

(77-4

I)(Sia)pi

(CHz),CH-CH,

2)H,02, NaOH (75%)

They also achieved an enantioselective synthesis of both the enantiomers of 91, employing (S)-prolinol as the chiral auxiliary (Scheme 25 Alkylation of

-

(S)-(t)-Sl(80%e.e.) [aJD28+4.260(CHC13)

4 d(CH,)90Ac

C

(30.40%)

Scheme 251

(R)+).Sl (92% e.e.)

[alDmat reported

120

The Synthesis of Insect Pheromones, 1979-1989

the dianion of A gave (S)-(+)-B, while that of the anion of C yielded ( R ) (-)-B. Sonnet's other synthesis employed optical resolution of the acid A via amides B and C as the key-step (Scheme 252).336

H , N ~

'\i.

1)HCIOpq THF

(CH,),CH=CH,

Z)WIH,~HF

(845%)

-

299.6% 8.8.

(CH,),CH=CH, C

-

3)recrysfnor HPLC sepn (32.40%) l)Ph3PBr.pH2Clz CH,OH P)(Sia),BWIHF 3)LiEW 4)H202,NaOH

h

(58.0%)

5)AcCVC,H,N

O

A

c

(S)-(t)-91 [a]D"t5.60a(CHC13)

(R)-(-).Sl [~],~-5.57~(CHCl,)

Scheme 252

Hjalmarsson and Hogberg also achieved a synthesis of the enantiomers of 91 (Scheme 253).337Their first step in preparing (R)-91 was the asymmetric

I

B

A

(z9B%e.e.)

2)2.Oeq BrMg(CH,),OTHP 3)TsOWMeOH

(9096)

(27%)

-

. .

&OH

1

D

(>w% e.e.)

Scheme 253

(fl)-(-)-€ll [a],a-5.B40(CHC13

-0Ac

f (S)-(+)-91

[a]:r5 9ZD(CHCI3)

11. Chiral Alcohols and Their Esters as Pheromones

121

ethylation of the amide A to prepare (R)-2-methylbutanoic acid (C) via B. For the preparation of (5’)-91, (S)-2-methyl- 1-butanol (D)was employed as the starting material. Brown et al. synthesized (R)-91 starting from (R)-2-butylthexylborane (A) (Scheme 254).338

- WeC H =HC M

@“z

dH NOW,

2pMeCHO

”‘%

1)NaOH

d k H ) z

+it

11Ii=-

&&

H

2)’2

3)H202,NaOH

A 99% 8.8.

4)HFIMeCN

5)Ac,0/C5H,N (82%)

-

l)Sia,BH OAC

>

2)AcCJH

OAc

3)H2OZ,p~ 8 buffer

N,H,, CuW,

OAC

EIOH, air

(R)-91

( Q W

[a]Dn-5.930(CHCI,)

Scheme 254

Ceskis and Moiseenkov synthesized both the enantiomers of 91 (Scheme 255).33ySerebryakov’s synthesis of (R)-91 is summarized in Scheme 256.”’

-

&OH

F

1)TsCVC5H,N

2)NaBrlDMF

>

A& + -

1)Mg

(80%)

-

HO,C

AoAc b

O

&OAC

A

i

OAc

1)HdPd

Pb(OAc),

Cu(OAc),

-.

2)A&$H,).OT6 Li,CuCI, (65%)

2)KOH

c

(R)-91

~U]~-~.W~(CHCI~

Scheme 255

A

O

A

c

122

The Synthesis of Insect Pheromones, 1979-1989

THF, E$O LI2CUCI, (R)-91

-2.6 (CHCI,)

Scheme 256

-

A simple synthesis of (*)-91 was reported by Horiike et al. (Scheme 257).”’

do +

NaH Ph,P’(CH2),0H.Br’-->

A%O/C,H,N

\

DMSO (55%)

OH

(88%)

L. (S)-1-Methyldodecyl Acetate 92 (C 15H3002) Aggregation pheromone components of Drosophila mulleri are (S)-( +)- 1 methyldodecyl acetate (92) and (Z)-I O-heptadecen-2-0ne.~~~ Both the enantiomers of 92 were synthesized from the enantiomers of ethyl lactate (Scheme 258). 342

M. 1,2,6-TrimethyltetradecylAcetate 93 (CI9H,,O2) and 1,2,6Trimethyltetradecyl Propanoate 94 (CZOH4002) Pine sawflies belonging to two genera (Diprion and Neodiprion) employ the acetate 93 or propanoate 94 of 3,7-dimethyl-2-pentadecanolas their sex-attractant p h e r ~ m o n e . ~ ~ ~ . ~ ~ ~

11. Chiral Alcohols and Their Esters as Pheromones

?H

OTHP

123

Me(CH,),MgBr

AC0,Et PPTS. CH,CI,

2) TsCVC,H,N

Li,CuCI,TTHF (50%)

Baker et al. reported two syntheses of a diastereomeric mixture of (*)-3,7dimethyl-2-pentadecanol by utilizing the product of the palladium-catalyzed reaction of 1,3-butadiene with diethyl rnalonate and that of the nickel-catalyzed reaction of 1,3-butadiene with acetaldehyde (Schemes 259 and 260)."'

(96%) 1) NaH. LiAIH,IDME (55%)

C02EI

2) PBrJother(7iX)

NaH,Br -OTHP DMF(46%)

A 1) LiAIH,

o

2) NaH. BnCl

HMPA 1 1o0c

(56%)

Scheme 259

0

3) TsOHlMeOH 4) CBr,. Ph,P

OBn B

124 @

The Synthesis of Insect Pheromones, 1979-1989 +CH,CHO

,

-

0

1) NaH

ek /THF (57%)

O h +

v

M

g

E

preepd horn A

B

r

A

1) LlAIH,/efier

2) NaH. BnCl

2) NaH, MelITHF (71%) 3) NaCWHMPA (43%)

Er

-

___j 2) PEr,

Ph,P, ether (239% with respeclto Ni)

J L C O F

yB

1) HdPdC

HO-

2) H20,, NsOH 3) PEr,

U2cuc14,

> -

&

THF (40%)

(3.93

Scheme 260

Another synthesis of (+)-3,7-dimethyl-2-pentadecanol was reported by Kallmerten and Balestra by the enolate Claisen rearrangement of allylic glycolates (Scheme 261).'46 Thus, the rearrangement of (&)-B (prepared from A) proOH &(CH2),Me

1) H, Rind.% Pd

2) EnOCH,COCI /C,H,N

(+)-A

(mx)

O & 'H '

(CH,),Me

6Bn

>-

4

L

i

Mg Br, /EbO

(72%)

1) LiAIH,

(53%)

(+,-a3

Scheme 261

11. Chiral Alcohols and Their Esters as Pheromones

125

duced (i-)-C stereoselectively. Similarly, D yielded E after the rearrangement, which was finally converted to the target alcohol. A synthesis reported by Serebryakov also used a rearrangement reaction (Scheme 262).347Serebryakov reported another synthesis of (IRS,2S,6RS)-93 (Scheme 263-1).348

-0,IPdCI,

--d

-

+t&Br

CUC$

THF

(70%)

(80%)

OH

PBr, /C6H6N

Br

+

(78%)

Br

I

(64%)

(as%)

AcCl /EbN

40

(*).as

Scheme 262

A new synthesis of (lS,2S,6S)-93 and 94 was reported by Norin et al. (Scheme 263-2)."' The chiral center at C-6 was provided by an asymmetric synthesis. Two other chiral centers originated from (+)-tartaric acid. Addition of B to D was the key-step, creating a mixture of E and F. A full account of Tai's earlier synthesis of (IS,2S,6RS)- and (IR,2R,6RS)-94 was published.350Tai's new synthesis of (1S,2R,6R)- and (IS,2R,6S)-93 and 94 employed two chiral parts, A and B, for the coupling reaction (Scheme 264).35'Ethyl (R)-citronellate was used to prepare A, while B was derived from (2S,3S)-2-methyl-3-hydroxybutanoicacid. Fujisawa and co-workers synthesized ( 1 S,2S,6S)-93, starting from sulfurcontaining 0-hydroxy esters obtained by the yeast reduction of the corresponding @-ketoesters (Scheme 265).352*353

-

0, PdCI,-Cu,CI,

Me(CH*)&W Cul lTHF (84%)

H,/Ni

,

(70%)

EZ-4: 1

Ac,O /EgN ~

W H

DMAP

(96%)

(92%)

(9.83

Scheme 263-1

1)TsCI /C,H,N

720A0.0.

(85%)

C02H

*

elher

l)CH2(CO2Me),. NaOMe

H:$?

MeOH

2)KOH / H 2 0

C0,H

D

3)conc.HCI

-8OOC

(53%)

(63%) NH , .,

+

KOH

HO(CH,CH,O),H

E

F

(lS,25, 65)-93(86%)

[Cl],”

6.6’ (neat)

Scheme 263-2 126

(76%)

( l S , 25. 6R)-93 (14%)

OH

&

11. Chiral Alcohols and Their Esters as Pheromones

i)03/MeOn

u

C

0

2

E

2) H, / PO, 3) UAIH,

2) H, /Pd

(quant.)

(29.5%)

1)H, /Ni modifiedwilh (S, S)-lar(arka&

>

2)Separalbn 01 diaslereomen 3)OpOcal enrichment01the @somer

1) NaOMe

+O,M

OH

2) n-BuBr

(W

>-

1) DHP. H'

6

0

-

2) UAIH,

l)Me(CH,),CH=PPh, OHC

t

(R)-(+)-Pulegone

0

127

OTHP

,

>-

+co,8"" OH

TsCI +OTs CAN

OTHP

B OAc

Li,CuCI,

A*0

(84.4%)

A'+@

> -.

Li,CuCI,

(25.3R. 7R) la],"+16 03' (hexme)

OH

-

(IS. ZR, 6R)-93 lalorn+6.97' (hexans)

_j

Larcheveque et al. reported the synthesis of (lS,2S,6S)- and (IS,2R,6R)-93, starting from ethyl (R)-3-hydroxybutanoate, D-serine, ethyl (2S,3S)-2-methyl3-hydroxybutanoate, and D-threonine (Scheme 266)."' Biochemical methods were employed for the preparation of the chiral hydroxy esters. Utilization of ~ e r i n e ~and ' ~ t h r e ~ n i n eis ~also ~ ~ noteworthy in this synthesis.

OAc

-

The Synthesis of Insect Pheromones, 1979-1989

128

&cop SM.3

bakets yeast (62%)

1) DHP. PPTS/CH,CI,

> WozEt OH

1)MCPeA

SMe

2) AI-Hg

OH

s

m >- .

(CH,),Me

5) TsCVCSH,N (76%)

1) DHP, PPTS

S

synC

EOH

-0Sn

4) TsOH/MeOH

+

(65%) 1) Raney Ni

THPOMeSSEt

> 3) NaH, BnBr, Bu,NI

VSM

bahehyeest

OTs

2) LIAIH,

(76%)

(3S)-A +96% e.e.

v

OH -CO2Et

( 94 : 6 )

(&6% e.e.)

,

2) Ac,OlC,H,N

Y

S

M

e

2) EtMgUHF-HMPA

anli-C

(>soh e.e.)

(lS,2s. 6S).93

(79%)

[a],”-10.5° (hexane)

Scheme 265

Among pine sawflies, species recognition is made possible by their use of different stereoisomers of 93 and 94. The white pine sawfly (Neodiprion pine” the red-headed pine turn) employs (lS,2S,6S)-93as its major p h e r ~ m o n e . ~To sawfly (Neodiprion lecontei), (lS,2S,6S)-93was again the active isomer.’s8 In the case of N . pineturn, the minor component (1S,2R,6R)-93was found to be a synergist.359On the other hand, the introduced pine sawfly in the U.S.A. (Dip r i m sirnilis) utilizes (lS,2R,6R)-94as the major component and (IS,2S,6S)-94 as a synergist.360 The European pine sawfly (Neodiprion sertifer) employs (iS,2S,6S)-93 as the major pheromone, also employing (lS,2R,6R)-93as the synergist.360Against Diprion sirnilis in the U.K.,both (lR,2R,6R)-94and its antipode were active.’“

N. 6,10,13-Trimethyl-l-Tetradecanol95 (C17H360) This is the aggregation pheromone produced by male stink bugs (Stiretrus anc h o r ~ g o ) .A ~ ~diastereomeric * mixture of all the possible stereoisomers of 95 was synthesized in 4% overall yield over 13 steps (Scheme 267) and shown to be b i ~ a c t i v e . ~ ~ ~

"

NHz 9 " Z H

OH

D-hreonine OH +CO,Et

-

(2S, 3s)-8

I

Sf

NeNOdKBr,HBr

A H20.-150C (9W)

+"ZH

>

CF,SO,H

CH,CI,

s"

e C O z E t

08"

>-

M,CuLi (61%)

EtO,CN=NCO,EI

Ph,P, hBr/THF

(M)=f.)

(94%)

(S)-A t (ZR, 3S)B

(95%)

(i-Bu)#IH

0

A C O Z E (

2)E5S04, 18cravn6

OH

-

CI,CC(=NH)OBn

I)KOHlEQH (85%)

(80%)

V

O h :

B

r

(2R. 3SpB

LDA

€50-HMPA (70%)

I ) NaHg. N%HPO,/MeOH (6G4'4

6h

2) H p d - C (86%)

3)Ac20/C,H,N

-> (IS, 23,65)43

(quanl)

OAc

[aJom 6'3 (hexane) (R)-A + (25,3S).B

LDA __j EbOHMPA (74%)

dSiPh21.BU

I ) Na-Hg. Nf@lP04/MeOH

(63%)

2) HF/MeCN-THF (62%)

3)Ac,O/C,H,N

(quanl)

Scheme 266

-> (IS.2R. 6R)-93 (a],mrg 3O (hexme)

OAc

129

130

The Synthesis of Insect Pheromones, 1979-1989

1) NaOEt

+s

?C02E1 >+

C

C02EI C02E1

-. ElOH

EOH 1) KOH

CO,H (75% horn C)

(S)-96

95

Scheme 267

0. (S)-1-Methltetradecyl Acetate 96 (C17H3402) This acetate 96 and 2-pentadecanone were identified as the major aggregation pheromone components in Drosophilu busckii. 363 2-Pentadecanone and (S)-96 were each active alone. The flies responded to (+)-96 but not to the pure (R)-96. The synthesis of 96 was achieved in the same manner as reported for 92 (cf. Scheme 258).342

12. PHEROMONE ALDEHYDES Many aldehydes are employed as insect pheromones. The syntheses of achiral olefinic aldehydes are discussed first, followed by the syntheses of three chiral aldehydes.

12. Pheromone Aldehydes

131

A. (SE,7Z)-5,7-Dodecadienal97 (CIZH200) This is the pheromone of the western tent caterpillar (Mefacowma culiforniA unique synthesis of 97 utilizing (formylmethy1)triphenyiarsonium bromide as one of the starting materials was recently reported by Huang et al. (Scheme 268).365 THPqCH,),CHO

+

[Ph$s*CH,CHO] &'

(7:3)

I'$O&O.THF

b'aca H,O (84%) 1) Me(CH,),P'Ph,W n-BuLflHF-HMPA 2) HCVaq MeOH

>

H OHC-C=C(CH,),OTHP

H

(CH,),CHO

>

H H H Me(CH,),C-C-C-C(CH,),OH H

> -

PCC CH2CI2 (68%)

(80%)

Scheme 268

Me(CH,),,

"C=C/

c=c'

d k

k

(5E, 72)-97 (98% pure)

B. (23-7-Tetradecenai 98 (C,,H,,O) The citrus flower moth (Prays citri) employs 98 as its pheromone. Brown's synthesis of 98 via boracyclanes is shown in Scheme 269. 12"

Scheme 269

132

The Synthesis of Insect Pheromones, 1979-1989

C. ( E ) - and (Z)-ll-Tetradecenal99 and 100 (CI4HZh0) The sex pheromone of the eastern spruce budworm is a 95 : 5 mixture of 99 and 100. A simple and economical synthesis of 99 and 100 as an 8 : 1 mixture was reported by Wiesner and Tan (Scheme 270) starting from oleyl alcohol.”‘ H H Me(CH,),C=C(CH,),OH

SOCI,

H H

1) OdMeOH

2) Me$, H’, Caw,

Scheme 270

D. (9Z,llE)-9,11,13-Tetradecatrienal101 (C14H220), (92,1lE)-9,11Tetradecadienal 102 (C 14H&), and (Z)-PTetradecenal 103 (C14H260)

The sex pheromone of female of the carob moth (Ectomyelois cerutoniue) is a mixture of 101, 102, and 103 in the ratio of 10: 1 : 1 ,367 Baker et al. synthesized 101 (Scheme 271).”’ PDC oxidation of (9Z, llE)-9,ll-tetradecadien-l-ol yielded 102.

E. (Z)-7-Hexadecenal 104 (C 16H300) This is the trail pheromone of the Argentine ant (Iridomyrmex hutnilis). Brown et al. synthesized 104 via boracyclanes in the same manner as shown in Scheme 269 for the synthesis of 98.”’ In the present case, 1-decyne was used in the second step instead of 1-octync.

12. Pheromone Aldehydes

H H H CH,~CHC=C-C&(CH,),O* H

H, C,

Et

=

H \ /C C, H

= C,I

102

H

't

,-

1) (n-Bu),NF

Si

I

2) PDC, MS/CH,CI,

133

(CHJ7CHO 101

p = C\Y

H\

(CH,),CHO Me(CH,),

(CH,),CHO 103

Scheme 271

F. (2)-11-Hexadecenal 105 (C16H3,,0) This is a common component of the sex pheromones of Lepidoptera, such as the rice stem borer (Chilo suppressalis), the cotton bollworm (Heliothis armigera), the tobacco budworm (Heliothis virescens), the iris borer (Macronoctua onusta), the diamond back moth (Plutella xylostella), and Leucania separata. Liu et al. prepared 105 by using the coupling reaction between 6-(tetrahydropyrany1oxy)hexylmagnesium bromide with (Z)-5-decenyl tosylate."' ( E ) - 10Hexadecenal was identified as the sex pheromone of the yellow peach moth (Dichocrocis punctiferalis) , 244

G. (10E,12E)-10,12-Hexadecadienal106 (ClhH280) This is the major component of the female produced sex pheromone of the spiny bollworm (Eurias i n s ~ l a n a ) . ~ ~ ~ Yadav et al. synthesized 106 by an acetylenic route (Scheme 272).17' Scheme 273 reports another synthesis of 106.'70

134

The Synthesis of Insect Pheromones, 1979-1989

H THPO(CH,),C=CC-CCH,CI H

EIMgI. Cul

H

THPo(CH,),ffiCC-C(CHz)~Me

EIpTHF

H

LiNHdNH,

Me(CH,),Br

Me(CHz)sGC(CH2)30H

(60%)

OHC-CIC(CH,)~OTHP

Me(CH,),P’Ph,Bi n-BuLi/THF

>

NaNH, H,N(CH,),NH, 80°C (67%)

>

M~(CH,),CH=CHCIC(CH~)~OTHP

(93%) 1) Li/NH,

> -.

2)Amberiile &OH (70%)

H,

1) l@xane H Me(CH,)zCH=CH-C-C(CHz)80H H 2) PCC/CHZCl2

> -.

H,

c=c’

Me(CH,)2/

(36%)

,(CH,)&HO C=C

k

k

106

Scheme 273

H. (11E,13E)-11,13-Hexadecadienal107 (C 16H280) The cabbage webworm (Hellula undulis) employs 107 as the female-produced sex p h e r ~ m o n e . ~Its ” synthesis was achieved by Arai et al.”’ by means of hydrozirconation reaction (Scheme 274).”* Lo and Shiao synthesized 107 in a simpler manner by a Wittig route (Scheme 275).”’ The dienol isomers A and B were separable by chromatography over silica gel impregnated with silver nitrate. Another synthesis of 107 by Yamada et al. employed alkylation of a sulfone as the key reaction (Scheme 276).

I. ( l l Z , 13Z)-11,13-Hexadecadienal 108 (C 16H2RO) The sex pheromone of the naval orangeworm (Amyeloistransitella) was obtained from ether rinses of the sex pheromone gland of calling females, and

12. Pheromone Aldehydes

1) Cp&rHCUC,H,

H,

2) IdC&

I'

c:c'

HCZC(CH,),~OTHP

H H EIC=C.C-C(CH,),,OTHP H H

>-

H

EIC-C'ZrCp~CI H

(CH2),,0THP

k

Pd(PPh,),/THF

H3

1) HaO'/MeOH

c:C:

(CH,),CHO

H*c:c~

2) PCC/CH,CI,

k

Et'

107

Scheme 274

PCC, NaOAc CH,C. I,

.

(66%)

H %=C' ' C d El'

k

k

107

- Scheme 275

0

I(CH,),,OTHP

Ell LiN(SiMeJ2

(CHz)~ooTHP

4

(48%)

H H EIC-C-C=C(CH,),CH,OH H H

>-

PCC,

(50%)

Alzo,

CH,C12

(68%)

H

c' = c'

"c' =c' El'

Scheme 276

k

107

(CHz),CHO

\

135

136

The Synthesis of Insect Pheromones, 1979-1989

was identified as 108.'74 Coffelt et al. synthesized all of the four possible isomers of 108 by a nonstereoselective route followed by HPLC and GLC separation (Scheme 277).374 OHC(CH,),,OTHP A

H P - 2 NI

I

>

H H EIC=CCH20H

1) PBr&,H,N 2) Ph.P

>

EtC=CCH,P' H H Ph,Br'

(.W H EC-CCH,P'Ph,Br' H W B H

Scheme 277

-

Soon afterwards, Sonnet and Heath published a stereoselective synthesis of

108 via an acetylene route (Scheme 278).'75 They purified the diynol B by

recrystallization.

0

I ) HCI HO(CH2),00H ___)

2,

I

H'

Cl(CH,),,OTHP

LIGiCH

Nal. DMSO (75.rnO)

HCnC(CH,),,OTHP A

H. H C: C: ,(CH,),CHO El( C:C. H' H (08

(>OQ.5% pure)

Scheme 278

Michclot's synthesis of 108 employed tetrakis[triphenylphosphine]palladium as a catalyst for cross-coupling (Scheme 279). I l7

12. Pheromone Aldehydes

137

(98%)

H HH H > EtC&-C=C(CH,),,OTHP

[Ph,PLPW,H,

IC-C(CH,),,OTHP H H

X m

(40.70%)

H,

1)TsOWaq MeOH

CtC:

Et'

2) PCC-AIzO~CH2CIz

H

c:c'

d

(CH,),CHO

H '

(79%) 108

(112,132):(1 12,13E):(1 1 E. 132): (1 1 E,13E) 1 3 :

:

- 8 3

3

1

:

Scheme 279

Bishop and Morrow reported a large-scale synthetic process of 108 (Scheme A noteworthy step in the present

280), by which they prepared 2.8 kg of

H,C=CH(CH,),OH

Brz CH,CI,

_ -

A

>

CH2BrCHBr(CH2)oOH

1) ElMaBrflHF I

H H ELC=CC&(CH,),CI B

liq NHJTHF

HC-C(CH,),OH

(78% lrom A)

MeSO,CI C,H,N/DMF (62%)

>

NaNH,

HC=C(CH,),CI

-

CH,=CHCHO

>

-

b,CUCI,

OAc

(67%)

WTHF

(45%)

1) MgfiHF

E1C.C-C=C(CH,),CI

2) AcOH, A

MeMgBrflHF

HzC=CH~HC&(CH,),CI

2) Ac,O/C,H,N

3) H20z, NaOH

2) HC(OEl),

C

(65%)

4) urea inclusion

(70%)

EtC-C-C-C(CH,)pCH(OE~)z H HH H

H .. ""zH

(97%)

I

C ' =C:

> El'

..4 C=C

H' 108

Scheme 280

,(CH,),CHO

k

(llZ.132):(112, 13E)

=

w.0

;

3.5

138

The Synthesis of Insect Pheromones, 1979-1989

synthesis was the selective inclusion of C by urea as the mild purification method of a labile diene such as C. Although the chlorodiene C was readily convertible to a Grignard reagent, the chloroenyne B proved to be inert toward magnesium even by entrainment techniques. Taylor and his co-workers employed the Normant reaction (acetylene carbocupration followed by electrophilic trapping of the resulting cuprate) for the synthesis of 108 (Scheme 281)377by a short and relatively efficient route. Their

108

(33% overall yield)

Scheme 281

detailed experimental procedure, including the apparatus used for double acetylene carbocupration, has also been published.37M

J. (4E,6E,112)-4,6,1l-Hexadecatrienal 109 (C IhHZhO) This aldehyde and (4E,6E,1 12)-4,6,11-hexadecatrienylacetate were the major components of the female-produced sex pheromone of the eri silkworm (Sarnia cynthia r i ~ i n i )Bestmann . ~ ~ ~ et al. synthesized these two compounds by a palladium-catalyzed cross-coupling reaction of vinyl halides with vinylstannanes (Scheme 282)."'

K. (Z)-11-Octadecenal110 (C,8H340) A species of the wax moth (Achroia grisella) employs 110 as its sex pheromone. It is also the minor component of the pheromone system of the spotted bollworm (Earias vittella), in which 106 is the major component. Ranganathan's synthesis of 110 (Scheme 283) started from methyl 10-undecenoate A, which can be prepared from castor oil."" The intermediate B was also con-

12. Pheromone Aldehydes

139

Me(CH,),CH=PPh,

H2C=CH[CHz)8C0,Me

1) LIAIH,

>-

2) DHP. PPTS

A

OHC(CH,),,OTHP

2) PCC. NaOAc/CH,CI,

(85%) 1) Ph,P=CBr, ____) 2) Li-HgEhO

(72%)

HCeC(CH~)foOTHP

E

(37%)

1) PPTSEDH

Me(CH,),~C(CH,),,OTHP

1) BHjTHF

>-

H,C=CH(CH,),OTHP

> --

*) H P d - e a s d

n-BuWHF

Me(CH,),&/HMPA

(94%)

H,

M~(cH,),’

quinoline-MeOH 3) PCC/CH,CI, (91%)

c=c‘ \(CH,),CHO 110

( 4 8 % pure)

Scheme 283

verted to several other pheromones, such as that of the Egyptian cotton leafworm (Spodoptera littoralis). Yadav et al. prepared 110 by a conventional acetylene route (Scheme 284).””‘) L. (2)-13-Octsdecenal 111 (CIRH340) The rice stem borer (Chilo suppressah) is a serious pest of rice in Asian countries. Its female-produced sex pheromone is a 5 : 1 mixture of 105 and 111.

140

The Synthesis of Insect Pheromones, 1979-1989

DHP, TsOH

HCeC(CH2),,OH

CHzC4 (95.8%)

1) UNHPH,

HC=C(CH,),OOTHP

m(CH2),b

2) Amberlile/MeOH

(7W

Scheme 284

Bestmann et al. synthesized 111 by a Wittig route (Scheme 285).’8’ Their starting material was either methyl etucate or methyl brassidate.

Scheme 285

Kang et al. reported a different synthesis of Bestmann’s intermediate, the aldo ester A‘ (Et instead of Me), starting from tetradecanedioic acid (Scheme 286) .382

12. Pheromone Aldehydes

141

M. (4R,SR)-4,8-Dimethyldecanal (Tribolure) 112 (C 12H240) Suzuki isolated and identified the male-produced aggregation pheromone of the red-flour beetle (Tribolium castaneum) as 4,8-dimethyIde~anal."'.~~~ The confused flour beetle, (Tribolium confisurn) also employs 112 as the aggregation pheromone. Recently, Suzuki et al. identified the aggregation pheromone of T. freemani as 112, and named it "tribolure. "3x5 To confirm the proposed structure, Suzuki synthesized a mixture of all the possible stereoisomers of 112 (Scheme 287).384His synthetic sample was about 10 times less active than the natural 112.

(46%)

112 (2.5mp)

Scheme 287

Another synthesis of a stereoisomeric mixture of 112 was also reported by Suzuki (Scheme 288).386He prepared not only 112 but also its several analogs, and found only 112 to be attractive against both Triboliutn casraneum and T.

142

The Synthesis of Insect Pheromones, 1979-1989

Scheme 288

confusum at the dose of 100 ng per disk.”‘ Later, however, Mori et al. found 2,6-dimethyloctyl formate to be almost as active as the stereoisomeric mixture of 112.387 A simple synthesis of a stereoisomeric mixture of 112 was achieved by Breuer et al. (Scheme 289).388They utilized the Julia cleavage of cyclopropyl alcohols

a,,, <

112

NeHCo3

&Br<

HdPo2

hear

(26OA)

A

AeOH

DMSO

B

(85%)

Scheme 289

as the key reaction to produce A. A slightly shorter synthesis of 112 from A via B was later reported.”’ A unique and selective synthesis of (k)-syn-112 was reported by Schreiber and H u h (Scheme 290).38yA group-selective dealkylation reaction of a bridged acetal A with trimethylsilyl iodide served to control stereochemistry at the chiral centers that are separated from each other. A synthesis of a diastereomeric mixture of 112 was reported by Odinokov et al. starting from 1,5-dimethyl-l,5-~yclooctadiene (Scheme 291).”’O Mori et al. achieved a synthesis of all of the four possible stereoisomers of 112 (Schemes 292-294).3y’Their strategy was to couple two chiral building blocks by sulfone alkylation, Grignard coupling, or mixed Kolbe electrolysis. Bioassay of the stereoisomers of 112 revealed (4R,8R)-112 to be as potent as the natural p h e r o m ~ n e . ~ Suzuki ” ~ ~ ~ ~et al. later found that a mixture of (4R,8R)-112and (4R,8S)-112 in a ratio of 8 :2 was about 10 times more active than (4R,8R)- 112 alone.3‘)4

A

I (89% Iran A)

MeOH

1)cat BySnCI, AIBN, 1.5 eq NsQH, (95%) 2) DlBAL (53%) 3) TsOH/MeOH (78%) 4) HdPIO, (77%) 5) TsCl(70%) 6) 3 eq Me,C~LiiE40 (84%)

>

I

0

(91%) (*).I12

+OM9 OMe

Scheme 290

(f) .112

Scheme 291 1) Ph,Se.JCH,CI,

HO ,,

>

3) I-BuOOH

HO / J y . . O C H z p h

N2H,, KOH HO(CH,),O(CH,),OH heal

&SO,Ph

1) TsCVC,H6N (want) 2) NaVMe,CO (86%)

>

1103

-OCH2Ph OH

2) NaBH,

A O C H , P h A

\/LCOzH& Pb(0Ac)4'CC'4 Ic hv

n-BuLDHF.HMPA

A /THF. -7OOC

>

I

PhSNa EIOH (55%)

>

&SPh

MCPBA CH,CI,

>

LirEINH, *OCHzPh SO,Ph

(82%)

45OC

(30%)

(4R.8R) -112

[slop.' -7.37' Scheme 292

(CHCI,)

143

144

The Synthesis of Insect Pheromones, 1979-1989

Li2CuCI,/lHF

A

(70%)

uoH > 1) TsCVC,H,N

Z)NaCN/DMSO

CrO, CH, -C,CHI,,N

3)NaOWELOH

&CHO

. .

( 1 1% horn A)

4) UAIH,

(4R,BS)-112 [a]02't9.94' (CHCI,)

Scheme 293

HCIO, sq THF

(3l%hOm 6)

>-

i

HO

(4S,8S) -112

Scheme 294

In order to supply an additional amount of (4R,8R)-112 and (4R,8S)-112, Mori et al. developed another synthetic route via mixed KolbC electrolysis (Scheme 295).395The overall yield of (4R,8R)-112from (R)-citronellic acid by this process was 8 % . A further need of (4S,8S)-112 and (4S,8R)-112 for biological studies motivated Mori et al. to prepare them via sulfones (Scheme 296).396 This route produced (4S,8S)-112 and (4S,8R)-112 in a 14-17% overall yield from (R)ci t ronellic acid, Another synthesis of (4R,8R)-112 by Fuganti et al. (Scheme 297) started from (S)-3-(2-furyl)-2-methyl- 1 -propanol, which is a bifunctional chiral Cs building block prepared by means of yeast red~ction.~" Moiseenkov and his co-workers prepared (4R,8R)-112 and its (4R,8S)-isomer by connecting two chiral building blocks (Scheme 298).3'8."9

12. Pheromone Aldehydes

1

I

. -C02H NaOMelMeOH

.

145

[a],*' -7.22' LCHCIJ

(5 9)

PI slecvode)

HCIO, aqTHF

~

OMe

(47.5%)

(69%)

>

CHO

(4R.8S)-112

Scheme 295

DHP

HodC02Me

i

7T H P o d C O , M e

UAIH (e5x;

>

TH~O-OHf

(01%)

1)TsCUC,H,N 2) MeMgBr. Li,CuCI,> (93%)

(4S.8R) -112, ' : l a [

Scheme 296

-e.B0(CHCI,)

U,CuCI,fTHF (59%)

[a],20-7.0' (CHCI,)

Scheme 297

U (77%)

O

A

c

2) KOH

>

(97%)

1) n-BuLi, Tact, 2) NaBr

(SW

lalo -7.0' (CHCI,)

Scheme 298 146

[alp+10.9° (CHCI,)

12. Pheromone Aldehydes

147

Starting from (R)-5-acetoxy-4-methylpentanoicacid (A) and (S)-3,7-dimethyl-I ,6-octadiene (B), Serebryakov and his co-workers achieved a synthesis of (4R,8R)-112 (Scheme 299).400 They also reported another route to &OAc

'b(OAC)4

HO,C

Cu(OAc),

> &OA~

'IKoH

(60%)

4

JCOTS

>

2) n - b L i , TSCI

C

3) HJPd.C

*

[alDz,' -7.37'

&p ;hL ,

>

1) n-Buli/THF

'".W K

(CHCI,)

-3

\

(4R,BR)-112

[alDP - 3 . d ' (CHCI,)

Ox"

Scheme 299

(4R,8R)-112 with 52% e.e., starting from enantiomerically impure (S)-3,7-dimethyl-1,6-0ctadiene.~~' Their synthetic 112 and analogs were tested against T. confusurn, and (4R,8R)-112 was confirmed to be the most potent attractant.402 Recently, Serebryakov reported a modification of his earlier synthesis of (4R,8R)-112 by using the Wittig reaction for the connection (Scheme 299).403 Suzuki et al. reported a synthesis of (4S,8S)-112 as shown in Scheme 300.404 a

C

O

z

H

U

C

H

O

OH

> *

-i

,

MCPBA (58%)

4

'

l)TsCI/C,H,N 2)LAlH, (41%)

(58%)

,01"

(65%)

>

*CNO (4S.8S) -112

[alD2'+7.73' (CHCI,)

uBr ' WE50

U

C

O

,

M

e

i,LiAIH,(70%)

2) 48% HBr (49%)

~

2) HC(OEt), 3)H30*

Scheme 300

(31%)

U

C

H

(4S.8t-6) -112

O

148

The Synthesis of Insect Pheromones, 1979-1989

They also synthesized (4R,8RS)-112 and several analogs of 112, and assayed them to confirm the strongest attractivity of (4R,8R)-112.4"" Randad and Kulkami described a synthesis of (4RS,8S)-112 starting from (R)-7-hydroxycitronellal(Scheme 301).405

KOAc I DMSO-H,O C02EI

(@%)

1) L~AIH, (we)

CHO

2) PCC /CH,CI, (88%)

(4RS,8S).112

Scheme 301

N. Faranal [(3S,4R,6E,l0Z)-3,4,7,1l-Tetramethyld,lO-tridecadienal] (C17H300)

Ritter et al. isolated and identified faranal (113) as the trail-following pheromone of the worker Pharaoh's ant (Monomorium p h a r ~ o n i s ) . ~Its " ~detection threshold is ca. 1 pg/cm of a trail. Kobayashi et al. synthesized all of the four possible stereoisomers of (6E,lOZ)-113 (Scheme 302).407The unique feature of their synthesis was in the use of farnesyl pyrophosphate synthetase for the construction of the chiral center at C-4. Another chiral center at C-3 was generated nonselectively, but the isomers were separable by chromatographic means. Bioassay of the isomers indicated (3S,4R,6E, 102)-113 to be the natural pheromone. Mori and Ueda carried out the synthesis of both (3S,4R,6E, 102)-113and its (3R,4S)-isomer (Scheme 303), and found (3S,4R)-113 to be b i o a c t i ~ e . ~ ~ ~ . ~ " ~ Both the chemical and enantiomeric purities of the products obtained by this synthesis was ca. 90%, and the final purification of 113 was carried out by preparative GLC to secure purer samples. This defect was due to the incomplete resolution of the hydroxy acid A to give lactone enantiomers B of ca. 90% e.e., and also due to the contamination with the (Z)-isomer of C. An asymmetric synthesis of (3R,4R)-lactone B was later reported by Enders (Scheme 304).4'0 Two syntheses of faranal 113 by strategies slightly similar to those of Mori and Ueda, but resulting in the preparation of its racemate, were reported inde-

12. Pheromone Aldehydes

149

E = Famesylpyrophosphale synlhemase A

C

1

I ) Et$H 2) H30' (Ph,P),RhCI 3) TLC. LC. GLC wparabn

>

W

C

H

+

O

*CHO

(3S.45)-113

1

(3R,4S)-113

L

C

H

(3R,4R)-113

O

+

U

C

H

O

(3S,4R)-llJ

Scheme 302

pendently by British groups. Baker et al. synthesized (f)-113 as shown in Scheme 305.4"*412In their synthesis, the E-double bond at C-6 was constructed stereoselectively by alkylation of the alkenyllithium derived from A with bromide (k)-C, which was prepared from Mori's intermediate ( f ) - B . Knight and Ojhara employed the Wittig reaction for the construction of the C-6 double bond (Scheme 306).4'3.414 Starting from Mori's intermediate ( f ) - B , phosphonium salt (*)-D was prepared via half ester (+)-C. The Wittig reaction between A and the phosphorane derived from D produced a mixture of stereoisomers ( E : Z = 46:54). Separation of (f)-113 from its (6Z)-isomer was finally achieved by preparative GLC. Szantay's synthesis provided geometrically and enantiomerically pure 113 for the first time (Scheme 307).415*416 The key building blocks in this synthesis were (6Z)-homogeranyl bromide (A) and (S)-3-methyl-5-pentanolide(B). The latter was prepared by enzymatic production of a chiral half ester (methyl hydrogen 3-methylglutarate) from a prochiral diester (dimethyl 3-methylglutarate). As shown in Scheme 307, the synthesis was convergent, and proceeded in 1.9% overall yield from geraniol.

I

1)EIOH. HBr

Ho&COzH (12%)

(3S.4S)-B

(EIO)zPOCHMeCOzEl

OH

NaOEVDMF

>

'

EIO,C

'-

1

153%) . .

(E)-C

\

>

LSOzPh

n-BuLilTHF-HMPA (92%)

2) 1)TsC"C5H5N NaCNfDMSO

85%

'

15%

(2)-C

GOTH, ~)L~~EINH,-THF

~

21 TsOHlMeOH

uo l);Cl;,H,,N.HCI

(67.5%)

>U

C

N

f

(96%)

~~~~~> 3) LiAIH,

i

(72%) 2) GLC purilicatian

(90%)

(3R.45).113

(3S.4Sj.B

(35.4R)-113

(a]Dn.16.40 (nbxana)

la],n +16.2' (n-hexane)

Scheme 303

(65%)

(59%)

Scheme 304 150

(3R,4R)-B (Scheme 303) 296%ee 2 96% d e

b , (74%)

LB

1) MeCu[Me,SlMgErl 2) Iz (49%)

LiC=CH*HzN(CH,)2NH2 DMSO

(70%)

I) 2 eq l.BuLYE$O

2) ( f ) . C n H F

1) TsOHMeOH

>

OTHP 2)PCC/A120,

(78%)

A

> (3R'.4S')(k)-113

Scheme 305

l)KOH/aqElOH

2) Ph,P/C,H, 170%)

+C02M

46

>

* .IPh,P + +COzH

(fP

+

54

A1)>2 eq NatilDMSO (64%) 2) CH?N2

I) LiAIH,/Etz0 2) PCClCH CI c o z ~ e 3) prep GLC?stpn

'

152

U

The Synthesis of Insect Pheromones, 1979-1989

O

T

H dH,OMs

P

1) LiAIH,/THF(O%)

2) TsOH/MeOH(94%)

OH

PDC/CH,CI,

(65%)

(3S.4R.6E.I0Z)-113 +17.P0 (CHCI,)

Scheme 307

0. (R,Z)-Trogodermal114 and (R,E)-Trogodermal115 [ 14-Methyl-8-hexadecenall (C ,,H3*0) Dermestid beetles (Trogoderma species) and khapra beetle (Trogoderma granarium) employ trogodermals 114 and 115 as the female-produced sex pheromone. (R)-Trogodermal is the bioactive e n a n t i ~ r n e r , ~ " -although ~'~ Rossi et al. claimed the (S)-isomer to be more b i o a c t i ~ e . ~ ~ ~ . ~ * ' Synthesis of both 114 and 115 by Rossi et al. is shown in Scheme 308.42' They started from (S)-( -)-citronello1 (A) and employed the known alkyne Ccf.422.423as the key-intermediate. They claimed their (R)-114to be less bioactive than (S)-114,which had previously been synthesized by them.424Their (S)-114was reported to be active against the male khapra beetle at the dose of

A (Flub)

ESN-CH,Ch

1)

OH

2) LiAIH, / E$O

12. Pheromone Aldehydes

&

1) H,O,-HC0,H 2) NaOH / EtOH 3) HI0,.2H20

LiAIH, / EhO (92.4%)

Lc02H

THF

(70.7 %)

’

153

4) AgzO/ NaOH aq

(62.3%)

cno

\\

C

CHO

heal 185%) . . 2) PCC I CH,CI, (50%)

(R,E)-115 [ a ] ~ 5 4 . 0 4(ether) 0

Scheme 308

10-8-10-9 pg, while (R)-114 was active at 2 x lo-’ pg. This biological result was later disproved by lev in sot^.^'^ Mixed KolbC electrolysis was employed as the key reaction in the synthesis of ( E ) - and (2)-isomers of (R)-14-methyl-8-hexadecen-1-01 (E) by Jensen and Schafer (Scheme 309).425Starting from (S)-citronellol (A), the acid B was pre-

OH

A (Fluka. 8 4 % I ~ ~

HOC ,-

*

’ (@w

I)TsCVC,H,N

I)O@,CO

2) LIAIH,IE(~O

2) Jones CrO,

>

(78 4%)

B 1) KOHlMeOH

1) n-EuLffHF.HMPA

Ho2C
8 ’ . Pt eleckdc

2) H C V W H

2) Er(CH,),OTHP _. (76 3%)

(20.20h)

C

OH

D OH -115

(97%)

(R,E)-E

Scheme 309

114

’

154

The Synthesis of Insect Pheromones, 1979-1989

pared, which was then coupled with C to give D after deprotection. Reduction of D gave the alkenols E, which had already been converted (Rossi et a ~ ~ to " ) 114 and 115 respectively. Mori et al. synthesized enantiomerically pure (S)-114and (S)-115to precisely determine their biological activity. (R)-Pulegone was converted to the enantiomerically pure (R)-citronellol, which was converted to the target molecules shown in Scheme 310.426By employing these samples, pure (S)-114was

1) n&Li / THF.HMPA

NaNH2/NH,

-

i

'

Er(CH2),0THP

Er

OH

(78%)

1) H, I Lindar Pd (61%) 2) PCC I CH,C12( 68%) OH

-

>

C H -O

(S,Z)-114 [a]D2'+6.1So(CHC13)

1) UAIH, (70%)

2) PCC / CH,CI,

(69%)

CHO (S.E).115 [a]Dn+6.920(ether)

Scheme 310

found to be times less active than (R)-114.Similarly, (R)-115was 0.5 x lo3times more active than (S)-115.It should be added that (S)-114and (S)-115 induced very low but definite receptor potentials when recorded from the antennae of male khapra beetles. Sato et al. employed (S)-3-butanolide as the key chiral building block in their synthesis of 114 and 115 (Scheme 31 l).427 Bestmann et al. synthesized both (R)-114and (S)-114via optical resolution of 2-methylbutanoic acid (A) (Scheme 312).428The amide C prepared from A and (R)-phenylglycinol (B) could be separated by MPLC with a Lobar@' column. The resolved acids, @)-A and (S)-A, were converted to (R)-114and (S)-114. Bioassay of their samples on T. granarium confirmed the previous result: (R)114 was 102-103times more active than (S)-114.It should be added that (R)2-methyl- 1-butanol, the key-intermediate in the synthesis of (R)-114and 115, was synthesized by Brown et al. by their organoborane chemistry.429

-

HO w H

00

0

l)TsCVC,H,N

CHO

2) LiAIH, 3)dl HCI-Me,CO (70%)

(R,Z)114

-5 96°(CHCI,)

d O A OCul, THFMezS (95%)

(97%)

-

1) M W W

HO,C

i - -H r L

3)Jr0 2) Cul

/

0

O

O

U

(77%)

(M)%)

CHO

(R,E).itS

E.2 = 9:l

Scheme 311

[a],22-4 72'(elher)

L;Ph,& > 1) NaN(SiMe3flHF 2)OHC(CHZ)70THP

OTHP

(87%)

OH

Similarly

d C 0 , H

PCC/CH,CI,

[a],,"t6.9O0(eIher)

Scheme 312

(87%)

CHO

(82%)

(S)-l14

TsOHlaq MeOH

(f)

156

The Synthesis of Insect Pheromones, 1979-1989

Serebryakov and co-workers synthesized both (R)-115(Scheme 3 13)430and (R)-114(Scheme 3 14)43' starting from (R)-4-methylhexyl bromide.

3) U*CUCI, (71%)

OH

(91%)

'

OAc

A

dil HCI (9%)

'

CHO (R)-IIJ -2.aa

Scheme 313

(73%)

(62%)

(71%)

aq AcOH

(97%)

CHO

(R)-114

lalorn- I 7' (CHCI,)

Scheme 314

Schlosser and Strunk employed the Wittig rearrangement of ally1 ether A to aldehyde B as the key-step in their synthesis of (S)-114 (Scheme 3 15).432

13. Pheromone Ketones

A

(77%) 1) s.BuLi/ THF. -75'C 2) KOBU', -75--+25'C

3) Me,SiCI. Me,N(CH,),NMe, 4) NaOH aa

Ph,P &CHo

ONa THF

B

157

(76%)

>

(64%)'

HO-

-

>-

(Ski14

(aIDm +5.3' (CHCI,)

Scheme 315

P. 2,6-DimethyI-S-heptenal 116 (C9H160) This is the alarm pheromone of yellow ants (Acanrhomyops species). Serebryakov and Gamalevich prepared (f)-116 by means a Cope rearrangement (Scheme 3 16).433

%+

HO

H

H

ucHo

Scheme 316

13. PHEROMONE KETONES Many ketones are employed as pheromones. In this section, achiral ketones will be discussed first, followed by branched-chain chiral ketones and hydroxy ketones.

A. (Z)J-Undecen-2-one (C, IH,oO) This was isolated as the principal volatile component contained in the pedal gland exudate of the bontebok (Damaliscus dorcas dorcas). A number of syntheses have been reported .434-440 Because this is not an insect pheromone but a mammalian pheromone, these syntheses will not be detailed here.

158

The Synthesis of Insect Pheromones, 1979-1989

B. (Z)-lO-Heptadecen-2-one117 (CI7H3*0) Drosophila mulleri employs 117 as a component of its aggregation pheromone. This was prepared by treatment of (Z)-g-hexadecenoic acid with methyllithium. 342 C. (2)-12-Nonadecen-9-one 118 (C,9H3,0) and (Z)-13-1cosen-lO-one 119 (C20H380)

As two unsaturated ketones, 118 and 119 are the female-produced sex pheromone of the peach fruit moth (Carposia niponensis), which is the major economic pest of apples, peaches, and other fruits in Japan.441Since 1979 many new syntheses of 118 and 119 have been reported. Synthesis of both 118 and 119 by Vig et al. utilized the acetylene route (Scheme 317).442 Me(CHZ)5Br

LiC=CCH,OLi ___)

Iiq NH$ THF

Me(CH,)5C~CCH,0H

H2/ Undlsr Pd

>-

H H

Me(CH,),C-CCH,OH

quindine/ hexane

(50%)

(95%)

Similarly

118

Scheme 317

Yoshida and Saito prepared 118 and 119 employing acylation of a p-tolylsulfone as the key-step (Scheme 318), followed by the Wittig reaction.443Naoshima et al. also utilized the Wittig reaction to prepare 118 and 119 (Scheme 319).444The Wittig reaction was again employed by Hernindez et al. in the synthesis of 118 and 119 (Scheme 320).445

13. Pheromone Ketones

H30’

R

h

O

M

OMe

e (81%)

,

Ph3P=CH(CH2)shk

159

‘w 0

R&CHO (54%)

118 R=Me(CH,),119 R=Me(CH,),-

Scheme 318

1) NaH/ toluene CH2.CHCH2Br, Nal

0

0

(74%)

0 OHCAR

Ph3P=CH(CH,),Me (6244%)

C02El

DrO,.NaIO, R + THF.HzO

0

2) NaOHaq.

3) HCI

(85.86%)

(84.86%)

-

118 R=Me(CH,),119 R=Me(CH,),-

Scheme 319

0

Me(CH2),Li Me(CH,), (78%)

’

0

Me(CH,), L C boH CH,CI, PCC.NaOAc (98%)

118

Similarly

119

Scheme 320

H

O

Me(CH,),CH=PPh,

>-.

(40%)

160

The Synthesis of Insect Pheromones, 1979-1989

Sonnet reported one-pot conversion of alkynes to cyanoethylated alkynes and applied the method to the preparation of 118 and 119 (Scheme 321).446 1) n-BuLi/ THF Me(CH1)5CzCH A 2) m / H M P A

1) MsCl

>-2) NaCN/ DMSO

Me(CH,)5C~C(CH,)20H

0

Me(CHZ),C=C(CH,),CN B

(48% from A)

Similarly Me(CH,),MgBr

c=c' Me(CH,),'

\(CH,),C(CH,),Me 1IS

It

0

Scheme 321

Yadagiri and Yadav synthesized 118 and 119 by two successive alkylations on tosylmethyl isocyanide with appropriate alkyl groups, followed by hydrolysis of the resulting products to the ketones (Scheme 322).447 Me(CH,),CsCH

n.BuW BF,.EbO

7

Me(CH,I5C~C(CH,),OH

(85%)

1) HA P&CaCO3 ____j 2) MsCU EgN 3) Nall Me,CO

H\

c=c'

Me(CH,),'

(sex)

NC

'(CH2)J A

118 R-Me(CH,),119 R=Me(CH,),-

Scheme 322

Kochetkov and his co-workers achieved a short synthesis of 118 and 119 by the reaction of alkenylcopper(1) reagents with seleno esters (Scheme 323).448 A synthesis of 119 by Kang and Cho was based on organoborane chemistry (Scheme 324).449Kang explored three other routes for the synthesis of 119 (Schemes 325-327).450 Wenkert et al. prepared the (Z)-alkene part of 118 by the nickel-catalyzed Grignard reaction with dihydropyran (Scheme 328).451By this method of (Z)alkene preparation, they also synthesized muscalure (19) and (Z)-5-decenyl iso-

13. Pheromone Ketones

161

valerate, the female-produced sex pheromone of the pine emperor moth (Nudaurelia cytherea ~ y t h e r e a ) . ~ ~ '

E 9 (96%)

Similady :

I

(78%)

0

1 I

SiMe,

0

H\

Me(CH,),COMe

Me(CH,)f

=c'(CH,)2!(CH,),M, 119

Scheme 323

1) n-BuUI THF

/

roomtemp.

162

The Synthesis of Insect Pheromones, 1979-1989

NaCN Me(CH,),CHO

_____)

HCI

Me(CH2),CH

\ CN

(93%) OEE

LDA

I I

THPO(CH,),C(CH,),Me Br(CH,),OTHP

CN

(75%)

>-

0

II

PCC

/ OH

OHC(CH,),C(CH2),Me

CHz=CHoE’

\ CN

POCI, (103%)

0

1) H2S04/ MeOH

-

II

HO(CH,),C(CH,l,Me

2) 0.5N NaOH

(88%)

Me(CH,),CH=PPh,

”\c = c,“

Me(CHJS’

(74%)

(82%)

,

OEE

MeiCH,),CH

0

(1

\(CH,),C(CH,),Me 119

Scheme 326

Os04.Na10, (73%)

0 II OHC(CH2)2C(CH2),Me

Me(CH,),CH-PPh,

MeICH,):

H

‘c t;c:

H (CH,)2C(CH2)eMe

II 119

O

Scheme 327

In Kang’s 1987 synthesis, 2-nonylfuran was employed as the precursor to provide keto aldehyde A necessary for the construction of 119 by the Wittig reaction (Scheme 329).452The same keto aldehyde was prepared in a different manner as shown by Bhalerao and his co-workers (Scheme 330).453 Trehan et al. synthesized 118 and 119 by alkylation of appropriate metallo-

0

-

13. Pheromone Ketones

>- ,

H H Me(CHZ)5C4(CH2),0H

Me(CHZ)$MQBr

+

[Ph2P(CHz),PPhz]NiCI,

PDC

CH,Ci,

(85%)

H H Me(CH,)5C=C(CH,),CH0

PDC /

CH,CI, (93%)

- n-8uWTHF

1 ) Br,. NaHCOd MeOH

Me(CH,),Br

@(CH,)8Me

(74%)

2) H d PdG

TsOH

MaG&H2)OMe-

(96%)

(48%)

Scheme 329

CH,=CHCH,Br ZnlNt4,Cia.q

’

(45% overall yield)

>

OH

Z E= 9’1 110 R=Me(CH,), 119 R=Me(CH,),

Scheme 330

PCC

R

y HO

O

H

-

CH2C12

163

The Synthesis of Insect Pheromones, 1979-1989

164

1) LON THF

H H

“Me, 11 H H RCH,C(CH2),C-C(CH2),Me

2) Me(CH,),C=CCH,Br

“Me2 MCMe II

0 II

NalO,

RCH,C(CH,);

PH 7 phosphate buffer

3) L O N THF 4) ABr

‘(CHZ),Me

118 R- Me(CH,),.

(95.98%)

(72.78%)

H\c=cl“

119 R-Me(CH,),-

Scheme 331

hydrazones followed by hydrolysis (Scheme 33 Independently, Yamashita et al. prepared 118 and 119 by the same method.455 Bestmann and Schmidt developed an interesting route to 118 and 119 by using a reaction between Grignard reagents and ketenylidene triphenylphosphorane (Scheme 332).456 Me(CH,),MgBr

+ Ph,P=C=C=O

1) THF. heat

>-

Hzo

0

I1

Me(CH,),CCH=PPh,

(78%)

(CH201,

0

II

Me(CHz),CCH=CHz

(55%)

118

(48%)

A synthesis of 118 and 119 from furfural was r e p ~ r t e d . ~Both ” 118 and 119 were prepared in four steps from 1 -decyne and 1-undecyne, respectively ,458 Yamamoto et al. prepared both 118 and 119 from 1 , I-diphenyl-phosphoranium perchlorate (Scheme 333).459 1) l.BuOW THF

Qcq’ p(, \ph

(75%)

11

H H

_____3 Ph,~CH,),C=c(CH,),Me 2) Me(CH,),CHO/THF

II

1)n-BuWTHF

HH

Ph,PCH(CH,),C=C(CH,),Me

I

2) MeSSMe

SMe

(86%)

119

Similarly.

Scheiiie 333

118

13. Pheromone Ketones

165

D. (6Z,9Z)-6,9-Nonadecadien-3-one120 (C19H340) (3Z,6Z,9Z)-3,6,9-Nonadecatriene (61) and (6Z,92)-6,9-nonadecadien-3-one (120)are the female-produced sex pheromones of Peribatodes rhomboidaria, which is a pest in vineyards.460Buser et al. synthesized 120 in a manner similar to the synthesis of the peach fruit moth (Curposina) pheromones 118 and 119 (Scheme 334).460 Me(CH2)8C=CCH,Br + &MgC=C(CH2),0THP

CUCl

Me(CHZ),C-CCH,CEC(CHZ),OTHP

>--

(75%)

H H H H Me(CH,),C-CCH,C-C(CH,),Br

> -,

KCN

(63%)

H H H H Me(CH2),C=CCH,C=C(CH2),CN

1) Hz/ Lindlar-Pd

2) Ph,P Br,

(35%) H\ CZC’

I ) EtMgBr

>-

2) H+

Me(CH,),’

H\

c .c’

‘CH;

(55%)

,

0 \(CH,),CEt

120

Scheme 334

E. (Z)-6-Henicosen-ll-one 121 (C2,H4,,0) and (Z)-1,6-Henicosadien11-one 122 (C21H380)

These are the principal (121)and the minor (122) male-produced sex pheromone components of the Douglas-fir tussock moth (Orgyiu pseudorsugaru). Many new syntheses of 121 and 122 have been reported since 1979. Normant and his co-workers used organocopper and organomanganese chemistry to prepare 121 (Scheme 335). ‘ I 5 Thexylchloroborane was employed by Zweifel and Pearson for the synthesis of 121 (Scheme 336).46’ 1) I(CH,),CO,El

IMe(CH,),],CuLi

+ ZHC=CH

THF-HMPA, PLOEI),

>-

(87%)

Scheme 335

The Synthesis of Insect Pheromones, 1979-1989

166

..

121

(74%)

Scheme 336

Trost’s synthesis of 121 is based on his finding that isopropylmagnesium bromide in the presence of bis-(triphenylphosphino)nickel(II) chloride reduces vinyl sulfides to the corresponding olefins without overreduction; this 1 1-step synthesis provided 121 in 16% overall yield from A (Scheme 337).462

>-

heal Hash pyrolysis (57% lrom A)

Map0

4 ,

(CH,),Me

B

I)KF/aqMeCN

2) NsBH,/EtOH 3) OHP, TsOH

T

(68%)

(42% lrom C)

W

O

4 (CH2 13Me

121

16% overall yield from A

Scheme 337

Subba Rao et al. employed the Birch reduction and Eschenmoser cleavage as the key-steps in their two different syntheses of 121 (Scheme 338),463which proved to be quite efficient. A very short synthesis of 121 (Scheme 339) was reported by Fernfindez et al., although the geometrical purity of 121 was 2 :E = 9 :

13. Pheromone Ketones

b OMe

76 OMe

Na

EIOH

OMe

x 6

eq H,SO,

1) KNHd NH,

(96.gB%) MeOH,

(75.85%)

..

3) dl HCI-MeOH

121

(25% overall yield)

Scheme 338

no

M(CH,),Li

T>

0

II

Me(CH2)s C1CH2 4OH

Cr0,~C6H,N~HCI NaOAri CH,CI,

-78OC

(98%)

(83%)

Scheme 339

0

II

Me(CH2)9C(CH2)3CH0

167

168

The Synthesis of Insect Pheromones, 1979-1989

Yadav's synthesis of 121 involved alkylation of tosylmethylisocyanide followed by acid hydrolysis (Scheme 340).464

FernAndez reported another synthesis of 121 starting from furfural (Scheme 341).465

Sonnet's method of one-pot conversion of an alkyne to a 5-alkynenitrile was applied to the synthesis of 121 (Scheme 342), and gave it in > 30% overall yield .446 Murata et al. reported a synthesis of 121 starting from tosylsulfone A (Scheme 343).466Naoshima's synthesis began with diethyl 3-oxoglutarate and gave 121 in 35% overall yield (Scheme 344).467

13. Pheromone Ketones

121

Scheme 343

(78% lrom A )

(87%)

121 (>98%Z)

(35% Overall yield)

Scheme 344

169

170

The Synthesis of Insect Pheromones, 1979-1989

Wang and Chu reported a highly efficient synthesis of 121 by tri-n-butyltin chloride-induced intramolecular transfer reaction of lithium l-alkynyltrialkylborate (Scheme 345).2'4 H H H Me(CH,)4C=CCH2C=CH,

>-

943BN

H H Me(CH,),C.C(CH,),-B~

LiCeC(CH2)8Me

~

121 (54% overall yield)

Scheme 345

Ousset et al. claimed that they prepared 121 by an interesting route via an enol ether A (Scheme 346).468What they actually synthesized, however, was

Me,SiCI.Nal MeCN (70%)

0

+

I1

1) HO(CH,),OH.H+

Wp),C(CH,),Me E

+

2) IMe(CH,),C=C),CuLi 3) H,O' H H

'

0

H H 11 Me(CH,),C=C(CH,),C(CH,),Me

C

(75%)

0

0

It

H H 11 Me(CH,),C=C(CH,),C(CH,)~Me

OHC(CH,),C(CH,),Me D

121

Scheme 346

not 121 but C. Conversion of their intermediate B to D will complete the synthesis of 121 from A, because D is a popular intermediate for the synthesis of 121 (vide supra), Wenkert employed the nickel-catalyzed Grignard reaction with dihydropyran for the construction of the 2-double bond of 121 (Scheme 347).45'

13. Pheromone Ketones

171

Scheme 347

Sodeoka and Shibasaki found a new hydrogenation procedure for alkynes to give (Z)-alkenes and a,@-unsaturated ketones to yield saturated ketones using (naphthalene)tricarbonylchromium(O) catalyst, and employed this reaction for the synthesis of 121 (Scheme 348).469 Bestmann and Schmidt reported a unique four-step synthesis of both 121

0

1 I

0

II

Me(CH,),CIC(CH,),CCH,P[O~)~

1) NaWTHF

-2

2) Me(CH,),CHO (88%)

Scheme 348

0

11H Me(CH2),CIC(CHz),CC-CH(CH2),Me

172

The Synthesis of Insect Pheromones, 1979-1989

(Scheme 349) and 122 (Scheme 350) using the reaction of Grignard reagents with ketenylidene triphenylphosphorane as the k e y - ~ t e p . ~ ~ ~

Me(CH,),CH-PPh

CI(CHZ,,CHO

(75%)

5

1) M f l H F ___.) 2) Ph3P=C-C4

H H

Me(CH,),C-C(GH,l,Cf

3) HO , (72%)

0

11

HH

Me(CH2),C=C(CH,),CCH

-PPh,

Me(CH,),CHO

>

(52%)

0

I1 H

HH

Me(CH,),C-C(CH,),CC-C(CHz)~~

H

Scheme 349

+

leq Ph,P-CH(CH,),CH=PPh,

4

$6q

OHC(CH,),CI

H H

H H

sq Me(CHz),C=C(CH,)3C=C(CHz)3Cl +

&q 9

H H

CH,=CH(CH,)3C=C(CH,),CI

A

4

t

(48%)

eq CH,=CH(CH,),CH=CH,

1) M g H F

2' Ph3P;C=C=0

3) HzO

>

(65%) Me(CH,),CHO

(54%)

H H

>

teq+CHzDfn

0

11 H

CH2-CH(CH,),C-C(CH,),CC.CLCHz),Me H

4

H H

0

11

CH,=CH(CH,),C=C(CH,),CCH.PPh,

1) Cul/NaAIHJO(CH,),OMe),

2) H30'

(75%)

122

Scheme 350

Bis-alkylation of acetone N,N-dimethylhydrazone yielded 121 (Scheme 35 1) They then described an improved route to as reported by Reddy and both 121 and 122 starting from cyclopentanone N,N-dimethylhydrazone (Scheme 352).47'

13. Pheromone Ketones

HH Me(CHz),C.C(CH2)z0H

1) kCMSN'CH,CI,

2) U&lMe,CO

H H Me~CHz)~C~C~CHdzEr

(WX)

3) 2N HCI

(60%)

173

A

121

Scheme 351

1) CH,-CH(CH,),CH=PPh,

2) Cfl,'C,H,NHCI

(a%)

H.

c:c'

CH,-CH(CH,),

/

0

II

\(CH,I,C(CH,),Me

122

Scheme 352

Bhalerao and Dasaradhi prepared 121 as shown in Scheme 353.48The keystep was the solvomercuration of 1-dodecene and reductive carbon-carbon bond formation with methyl acrylate in the presence of sodium borohydride to give methyl 5-a~etoxypentadecanoate.~~ Yamarnoto et al. prepared a mixture of 121 and its (E)-isomer from a cyclic phosphonium salt (Scheme 354).472 Mitra and Reddy achieved a simple synthesis of both 121 and 122 in two

174

The Synthesis of Insect Pheromones, 1979-1989 1) Hg(OAo)JA,AoOH

Scheme 353

1) n-BuLlrlHF

1) n-BuLLTHF

(56%)

Scheme 354

steps using acetone dimethylhydrazone as the key starting material (Scheme 35q.473

Nishiyama's synthesis of 121 started from a cyclohexenone and utilized silicon-directed Beckmann fragmentation (Scheme 356) .208

1) n B u M H F

iNbz

2) hk(CH,),B(

h'mcb

3)n-BuLVTHF

[

'

13. Pheromone Ketones

1

[>H(CH,)3C(CHz),Me II

(79%)

175

(65%)

121

CH2-CH(CH,),CH-PPh3 THF.8al14ree

(74%)

122

Scheme 355

0Me3s1L!,

(CH,),Me

2) MeOH

6::; [:

> -TMSOTI

2) Ac,O/C,H,N

58

42

(CH,),Me

1) NH,OH HCI NaOAdEtOH

+

H H NC(CH,),C=C(CH,),Me

1) Me(CH,),MgBr

2) H,O'

(71%)

(88%)

H

>

SiMe,

'

Me(CH,),'

O

(CH,),CiCH,),Me

121

Scheme 356

F. (Z)-24-Tritriaconten-2-one123 (C33H640) This, together with 2-hentriacontanone and some other homologs, is the femaleproduced sex-attractant pheromone of the Canadian red-sided garter snake (Thamnophis sirtalis parietalis), which is not an insect; therefore, its pheromone chemistry will not be discussed here.

176

The Synthesis of Insect Pheromones, 1979-1989

G . (S)-4-Methyl-3-hexanone 124 (C7H140) The ant Munica mutica uses (S)-( +)-4-methyl-3-hexanone (124) as its alarm pheromone. Enders et al. reported an asymmetric synthesis of 124 by alkylation of a metallated chiral hydrazone (Scheme 357).474q475 Reaction of diethyl ketone

A (SAMP)

B

1) Me1 2) dil HCVpenIane

(6l%overallyield) (5).124 (94% e.e. )

[a],= +30.2O (€120)

Scheme 357

with (S)-l-amino-2-methoxymethylpyrrolidine (A, SAMP) yielded a chiral hydrazone B, of which alkylation was found to be highly enanti~selective.~~~,~'~ Brown et al. synthesized 124 (83 7% e.e.) by carbenoidation of a chiral borinic ester A (Scheme 358).476Another asymmetric synthesis of the antipodal (R)-124 H H I ) MeC=CMe 2) MeCHO

OEt

I ) UAIH, 2) CH,-CH:

a' 0 El

.L B (I,.

30% H202 (s)-124 (8wa.e.) [a)D" +25.16' (E(,O)

Scheme 358

(96% e.e.) was also achieved by Brown et al. by employing a chiral boronic ester A as the key-intermediate (Scheme 359).338 Optically active monoalkylthexylboranes such as B ( > 99% e.e.) are useful chiral building blocks in synthesizing a variety of optically active compounds.

13. Pheromone Ketones

a

B

H

,

H H

1) MeC-CMe

2

177

Hc

(EIO),B,,

2)2MeCHO

r OH

A

(R).124

8

(a],n

(96% e e ) - 3 0 . e ~ (EI~O)

70% overall yield lrom B

Scheme 359

H. (S)-4-Methyl-3-heptanone 125 (C8H160) The leaf-cutting ant (Atta texana) employs (S)-125as its principal alarm pheromone. Enders synthesized 125 (99.5 % e.e.) by his SAMP-hydrazone alkylation method (Scheme 360).474-475

R

O

i

M

e

- 1) LONE120

2) Me(CH,),I.-l lo°C (85%)

K

$H

O

M

e

1)Mel

++v2) dil HCVpenlane (8.?%)

(S)-125 (95.5% e.e. ) 4 20

(hexane)

Scheme 360

I. 3,6-Dimethyl-2,4-heptanedione126 (C9H,602) This is the female-produced pheromone of the mushroom fly (Megaselia halt e r m ) . Starting from 4,000 female flies, 30 pg of 126 was obtained. This pheromone exists as a mixture of the keto-enol tautomers in a 3 : 1 ratio; therefore, the chirality at C-3 is interchangeable. The synthesis of 126 by Baker et al. is shown in Scheme 361 .477

178

The Synthesis of Insect Pheromones, 1979-1989

126

Scheme 361

J. 6-Methyl-3-octanone 127 (C9H,80) This was identified as the alarm pheromone of ants in the genus Crematogaster. Naoshima et al. synthesized both the enantiomers of 127 (Scheme 362).478The overall yield of (R)-127 from (R)-Awas 26%, while that of (S)-127 from (R)pulegone was 14 % .

ElMgBr

CrOg

I

(67%)

0 (S)-127 1 ~ 1 ~ 2+IO.OBO 5

( neat, d 0.8244 )

Scheme 362

13. Pheromone Ketones

179

K. @)-Manicone [(4E,6S)-4,6-Dimethyl-4-octen-3-one] 128 (CloH180),Homomanicone 129 (C, ,H,,O), Bishomomanicone 130 (CI,H2,O), and Normanicone 131 (C9HI60) Manicone (128)is the alarm pheromone constituent of the mandibular glands in two North American species of ants, Manica mutica and M . bradleyi. It is also the main pheromone of M . rubida. Its absolute configuration was recently assigned as S by comparing dihydromanicone with synthetic (4RS,6S)-4,6-dimethyl-3-octanone employing the complexation GLC The synthesis of (4RS,6S)-dihydromaniconeis shown in Scheme 363.480In addition to

'

I POPh)

OH(-

EIC0,H

CO,H

LDA/THF-HMPA

CH,CI, (77%)

(60%)

EbCuLi

>

cocl

CHCI,

EI,O (57% lrom add)

0 (4RS,GS).dihydto-l28

Scheme 363

manicone (128), Bestmann et al. also isolated 129, 130, and 131 (128:129 : 130 : 131 = 100 :6 :0.3 :2.7) in the mandibular gland secretion of M. r ~ b i d aBestmann's . ~ ~ ~ synthesis of (f)-128,(f)-129,and (*)-131is shown in Scheme 364.480The Wittig reaction was fairly selective in giving (E)-128

4+++ 0

0

128 0

11

129

0

11 + EICCHPPh3Br

Ph,P

ElCCHBr

I

I

CSHS

Me

Ks

(60%)

0

131

130

0

(I

NaOH

toluene

EICC-PPh,

A

1 A,,,, /I I

(76%)

Me

(15%) E:Z=93.5.6.5

(55%)

Me3Si

I

Me-C=PPh,

+

0

E1COSiMe3 '1

MeCC=PPh,

(72%)

I

Me

d

C

H

10Iuene.

toluene

A

0

A

(18%)

Scheme 364

131 E:Z-93:7

0

129

(14%) E:Z=84:16

180

The Synthesis of Insect Pheromones, 1979-1989

and its higher (129) or lower (131) homologs, although the yield was rather poor. Nakai and co-workers prepared 128 starting from (8)-isoleucine (Scheme 365).48’Their key-intermediate was allylic thiocarbamate A readily derived from allylic alcohol B via the [3,3]sigmatropic rearrangement.

0

1) LDA.Me,SflHF

’

2) LDA,EIIflHF 3) HgO.BF,’EbO/aq THF

II

lalo”

. .

+39.60(CH2Cl2)

1) =I,

l)LDA.Me,SflHF,

“zH

2) HgCl,,aq MeCN

2)EbCuU

EbO

(85%)

’

(Sj.128

[alDm+38.8’ (CH,CI,)

(84%)

Scheme 365

Three ther synthes s of (+)-128 were report d. Conia et al. synthesized (&)-128by the addition of chloromethylcarbene to trimethylsilyl enol ether and

subsequent thermolysis of the addition product (Scheme 366).482Coutrot and

/d/

* OSiMe,

CI

CH,CHCI&BULVE~O

1) EtMgBf.CUMb0 2) Me3SiCVHMPA

> A

(78%)

loluene.reflux lodays (75% from A) &128

Scheme 366

Ghribi prepared (f)-128 using the Horner reaction with 2-diethoxyphosphonopropanoic acid dianion (Scheme 367).483A synthesis of (f)-128 by Yoneda et

13. Pheromone Ketones

181

Scheme 367

al. utilized their finding that enone cyanohydrin diethyl phosphates react regioselectively and stereoselectively with a variety of organocopper reagents to give (Z)-predominant 2-alkenenitriles as y-coupling products. Thus, the (2)-isomer of (+)-128was obtained as the major product (Scheme 368), which could be isomerized to (f)-128by treatment with

9 . 1 (f)-l?8

TsOH/C,H,

Scheme 368

L. (R)-lO-Methyl-2-tridecanone 132 (C14H280) This is the sex pheromone of the southern corn rootworm (Diabrotica undecimpunctata howardi). Sonnet synthesized both the enantiomers of 132 starting from 10-undecenoic acid involving the optical resolution of an intermediate (Scheme 369).336Male southern corn rootworms preferred (R)-132.4x5 Senda and Mori synthesized (R)-132starting from (R)-citronellyl acetate (A) (Scheme 370).486Although their starting material A was of 100% e.e., partial racemization might have taken place to a small extent at the stage of hydrogen-

The Synthesis of Insect Pheromones, 1979-1989

182

a

2) NaOH.NaQH,

(CH,)7CH=CH,

3) Na.p,O,-dil

H,SO,

(74%)

(S)-132

Similarly;

N,H,.KOH

1) 0.jNaHC03-MeOH A A (lW%ee.)

O

-> A

c

HO-OfiOH'

210°

(60%)

c

(82%)

+

1) TsCVC,H,N

2) Nal/Me,CO (60%)

-

8

HdPd-C

(41%)

cfl3

ElOH

(93.5%)

LiNHdNH3

(74%)

D

Scheme 370

KH.NH,CH,CH,CH,NH (KAPA)

(80%)

13. Pheromone Ketones

183

ation of alkyne C to alkane D on palladium-charcoal. This possible racemization was later pointed out by O p p o l ~ e r . ~ ~ ~ Rossi's synthesis of the enantiomers of 132 started from methyl hydrogen (R)-3-methylglutarate (A) (Scheme 37 l), and furnished enantiomerically pure

1) Hp(0Ac)daq THF

> 196%)

(65%)

(R)-I32

:]al

.l.M+O02'

(CHCI,)

1) HQ(0Ac)daqTHF

Me,CuLirE$O

OMS

(88%)

(68%)

Na,Cr,O,dil

40

(94%)

H2S0,

> (S).132

[a]? +1.65+002' (CHCI,)

Scheme 371

(R)- and (S)-132.488Serebryakov et al. synthesized (R)-132 from (S)-3,7-dimethyl-l,6-octadiene with an overall yield of 24-26% (Scheme 372).48' The key-step in Oppolzer's synthesis of (R)-132 was the asymmetric 1,4addition of propylcopper to the camphorsulfonamide-shielded crotonate ester (Scheme 373).487They avoided the racemization in the course of saturation of

184

The Synthesis of Insect Pheromones, 1979-1989

1) aq AcOH

'

1) NaBH,

ACHO

2)TsCVC5H5N

(83%)

(84%)

A

O

T

s

n

.o 0

BM~W (f34%)

(94%) (R)-132

[Ql,z'-1.64

(CHCI,)

Scheme 372

-

I

B (>99%de)

A

&OH

C

(8G%)

I ) UAIH,,CoCI/WIF

2)AcOH.H20

0 0

Ph3P

(COCI),,DVSO

H

O

THF

(85%)

a

n

0

0

\

i-

(78%)

(R)-132

[a],Z' -1 6io(CHCI,)

Scheme 373

the double bond by using lithium aluminum hydride in the presence of cobalt (11) chloride as the reducing agent. M. Matsuone [(2E,4E)-4,6,10,12-Tetramethyl-2,4-tridecadien-7-one] (C17H300)

The pine bast scales (Matsucoccus resinosae, M. matsumurae, and M. thunbergianae) use this compound as the primary component of their sex-attractant pheromones.490 A synthesis of this ketone has been accomplished,490 but the details are not yet available (March 1990).

13. Pheromone Ketones

185

N. (6R,12R)-6,12-Dimethyl-2-pentadecanone133 (C 17H340) The female-produced sex pheromone of the banded cucumber beetle (Diabrorica bafteara) was isolated and identified as 6,12-dimethyl-2-pentadecanone (133).49'Chuman et al. synthesized a diastereomeric mixture of 133, and the product was proved to be bioactive (Scheme 374).49'

Diaslereomeric mixlure 01 133

Scheme 374

All of the four possible stereoisomers of 133 were then synthesized by Mori and Igarashi starting from the enantiomers of citronellol (A).492 The terminal building block B was prepared from A by the known method (Scheme 375).4x6 Another building block was the phenylsulfone D,which was also prepared from A via C. The scheme shows the four possible combinations of the enantiomers of B and D that furnished all of the isomers of 133. Bioassay showed (6R,12R)-133to be highly active, while (6S,12S)-133was inactive. Both (6R,12S)-133 and (6S,12R)-133 were only marginally active.493

0. (3S,11S)-3,11-Dimethyl-2-nonacosanone134 (C21H420)and (3S,llS)-29-Hydroxy-3,11 -dimethyl-2-nonacosanone 135 (c2IH42O2)

These two ketones (134 and 135) are the female-produced wing-raising pheromones of the German cockroach (Blattella germanica). A full report of the synthesis (Schemes 249-252,Ref. 1) of all of the possible isomers of 134 and

186

The Synthesis of Insect Pheromones, 1979-1989 f

(W

(WE

W-A

OH

(SP

(96%ae,)

0

1) TsCI/C5H5N

(85%)

(69%)

MeO-(o]0 TsOH (93%)

'

1) 0,/NaHC03.MeOH \

2) NaBH,

(91%)

1) TsCI/C5HSN

2) Nel,NaHCOpe,CO

C

(82%)

-

1) n.BuLirlHF-HMPA

(59% lrom C)

dil HCI.MaOH

(92%)

(S)-B + (S).D (R).B

3

(6R.l2S).133

+ (RI-D 3

(6S,12R)-133

2

(65.125)-133

(S)-E + (R)-D

laJon + i 9' (CHCIJ

(6R,12R)-133

[a],"

-05'

(CHCI,)

.i9' (CHCI,)

lalorn

t o 5'

(CHCIJ

Scheme 375

135 was published by Mori et a1.494Bioassay of the isomers was carried out by Nishida and Fukami, who found even the unnatural isomers were as active as the natural (3S,11S)-134 and (3S,1 1S)-135.4'5 Jensen-Korte and Schafer employed the Kolbe electrolysis to construct the carbon skeleton of 135 (Scheme 376).496Their synthesis, however, did not ex-

(35.11S).135

(35,llS)-134 Br(CH,),,CO,H

+ HO,CICH,pJ,Me

>-

1) 8'. KOH I MeOH

2) KOH / MeOH ( 56% 1

0

H O , L C O , M e HO(CH2)t7C02H

1) e', KOH I MeOH 2) KOH / MeOH

( 39 %

13. Pheromone Ketones

187

tend to 135, but was abandoned at the stage of (3RS, 1 IS)-A. Katsuki and Yamaguchi achieved an asymmetric synthesis of (3S, 1 1S)-134 by using their chiral auxiliary A twice (Scheme 377).497

A

Me

1) LUIH.

H

1)PhCH2qCH,),Mgb

3)TsCI / CH ,N ,

( 6046)

4) Nal / MezCO 1) dil. HCI, heal 2) MeLi I Et,O

H

%I

Me H Me H

>

Me(CH2),,C(CHz),C

( 42% )

CMe

t:

Scheme 377

Mori and Takikawa developed a new synthesis of all of the four isomers of 100%e.e.) and ethyl (R)-3-hydroxybutanoate ( - 100% e.e.) (Schemes 378-380).498 The key-step (Scheme 379) was

-

134 starting from (R)-citronellol (

uoH 1) TsCl/ CH ,N ,

2) Me(CH,),,MgBr (R)-Ciuonellol

Li2CuCI,/ THF

1) 0,

2) NaBH,

> /bd(CHz)17Me 3) TsCI / C,H,N

(93% )

( 83% ) 1) 0, 2) NaBH,

-OMOM \

>

( 79% overall )

1) Me(CHZ),,MgBr

TsO&OMOM

3)TsCl/ C,H$ ( 79% )

Li,CuCI,/

THF

2)dil HCI 3)TsCl / C&N

(73%)

Scheme 378

188

The Synthesis of Insect Pheromones, 1979-1989 1) 2eq. LDA

Me1 ITHF-HMPA OH ~ C O z E l 2) 2eq. LDA ~THF

3) NH,CI aq

GTs +

( 96% )

4) EIOCH=CH,. TsOH (46% )

I

Nal. NaHC03, Me,CO ( 93% )

MeCOCH2COzMe &GO3 IMe,CO.DMF' ( 79% )

COMe

aq MeOH f 73% b

.

-

1) aq. AcOH ITHF

KOH

.

7

.

imidazoleI DMF

OH

( 81% )

TBSCl OH

( 87% )

( 40% )

Scheme 379

m p. 47.0.47.5°C.

Scheme 380

[a]g19 r5.52'

( hexane)

13. Pheromone Ketones

189

the chromatographic separation of (5RS,bR)-6-hydroxy-5-methy1-2-heptanone to give pure (5R,6R)- and (SS,6R)-isomers. All of the four isomers of 134 were confirmed to be bioactive.

P. Sitophilure [ (4S,SR)-S-Hydroxy-4-rnethyl-3-heptanone] 136 (CEH1602) Burkholder et al. isolated 7.5 pg of 136 as the aggregation pheromone of the rice weevil (Sitophilus oryzae) and the maize weevil (Sitophilusz e a r n ~ i s ) . ~ ~ ’ ~ ~ ~ ~ Its syn-(4S*,5R*)-stereochemistry was deduced by a synthesis of (f)-136 according to Smith (Scheme 381).50’ The diastereomers (4S*,5R*)-136 and (4S*,5S*)-136 were separated by preparative GLC.499.500

+

* 0

C;’H

LDA / THF

0

OH

0

MeCHO;78’C’ ( 45’35’ )-136

(4S’, 5R’ ).I36

( 89% )

( 4s. 5R ).136

Scheme 381

*-

Mori and Ebata synthesized all of the four stereoisomers of 136, starting from a single chiral building block A (Scheme 382).502Comparison of the ace0

8 QNO,

OH &COW

3-b

01. Scheme 400

1) KOH aq. 3) H2/ P 6 C

’

%OH

i

(QWk)

A

’

I ) (COCI 12’ O M S 0 Et,N I CH,CI 2)ElMgBr

3) chromalog. (SiO,)

( 100% a e

+dl0 &

+

i B( 52% )

L

C(21%)

(n;),NF

OHP PPTS ( 98% )

-

2) PPTS I MeOH ( 4s 55).136

( 652 )

( 88% )

>-

Milsunobu inversion

laJon+36.8(ESO)

+$io -CHO

_cj

cl. Scheme 4W

t

D( 20%) E

OHP

’

PPTS ( 97% )

0-

i

E ( 56% 1

2) Si0,chromatog.

1) Swern oxidation

2) (n.Bu),NF ( 67% )

1) Swern oxidation 2) PPTS I MeOH ( 88% )

1) ElMgBr ___3

Scheme 382

OH

190

The Synthesis of Insect Pheromones, 1979-1989

tyl lactate derivatives of the natural and synthetic samples revealed the pheromone of the maize weevils to be > 98%4S,5R, while that of the rice weevils was at least 92%4S,5R.503Bioassay also indicated (4S,5R)-136to be the major component of the pheromone of both S.zeamais and S. ~ r y e a e . ~ ~ ' Four other syntheses of 136 have been published since then. Fauve and Veschambre reduced 4-methyl-3,5-heptanedionewith a fungus (Geotrichum candidum) under anaerobic conditions and obtained the antipode of sitophilure [(4R,5S)-136]in unspecified yield (Scheme 383).5" Fuganti's synthesis of the

A

E1CO2EI NaNH,

'

Geolrichum candidurn anaerobic condihon

Scheme 383

natural (4S,5R)-136 is unique (Scheme 384),5"5employing the biotransformation of (&)-A to (3S,4R)-Bwith baker's yeast.506

( +). A

( f 5.20 % )

(

45% from C )

(3S.4R)- B

( 70% )

A'

(4s. 5R). 138

[aIDM t26 2

( ES0 )

Scheme 384

An interesting asymmetric synthesis of (4S,5R)-136was reported by Enders and Lohray (Scheme 385).507They first prepared (S)-a-silylketone B starting from the RAMP-hydrazone A of diethyl ketone.508 Subsequent diastereoselective and enantioselective aldol reaction between propanal and the boron enolate C yielded (4S,5R)-136 with satisfactory purity. Mori et al. reported a synthesis of 2.2 g of (4S,5R)-136by resolving (*)-A (Scheme 386) with (-)-w-camphanyl chloride.509The overall yield of this synthesis was 19%,and all of the intermediates were crystalline.

13. Pheromone Ketones

-n 0

0,I pentane ( 77% from A

,> +

B ( 2 96%

+

4 1 -

+ oB(n-Bu)z

( n-Bu)2BOS0,CF,

( i-Pr),NEt I CH2Cc .loor. 8.8 )

- -5 7- c

191

1) EICHO. -78OC

2) 0, 3) chromatog.

(45,5A). 136 ,264 ( E$O) 2 96% d.8.. 2 98% 8.8.

I a IDp

Scheme 385

Scheme 386

Q. (S)-2-Hydroxy-3-octanone 137 (C8H,602) This hydroxyketone 137 and (2S,3S)-2,3-octanediol (86) were isolated and identified by Sakai et al. as the male-produced sex pheromone of the grape borer (Xylotrechus pyrrh~derus).~'~ They synthesized (S)-137 by treatment of (S)lactic acid with pentyllithium (Scheme 387).3'2 Mori and Otsuka prepared

( S ). 117

Scheme 387

The Synthesis of Insect Pheromones, 1979-1989

192

(S)-137 employing the Sharpless asymmetric epoxidation as the key-step (Scheme 388). I 1) Ti( OP+)., (. ).DIPT

1) PhCH,CI. NaH / DMF 2) dil. HCI -THF

3)Jonos Cr03 (51%)

’

FHZPh

nu

H2I PBC EOH ( 59% )

0

(5)-137 [ .lom r66.8’ ( CHCI,) (92.94% e.e. )

Scheme 388

Davis et al. reported an asymmetric synthesis of (S)-137 (12% e.e.) by asymmetric oxidation of a lithioenolate B, which was prepared from bromoalkene A in a selective manner (Scheme 389).510Servi achieved selective oxi-

( 82% from A)

A

OH

MeLi / THF \so, -

0°C

0

(57%)

( S ).137 (12% e e j

Scheme 389

dation of the hydroxy group at C-3 of (2S,3S)-86 after protecting its less hindered hydroxy group at C-2 with 1 eq of t-butyldiphenylsilyl chloride. The monoprotected diol was oxidized and deprotected to give (S)-137 (Scheme 390).314Veschambre and his co-workers reduced octane-2,3-dione with bakcr’s yeast to produce (S)-137 in 71 % yield (Scheme 391).316 The biological study on the synthetic materials revealed (R)-137to be a phcromone i n h i b i t ~ r . ~ ”

1-EuPh2SiCI OH

OSiPh,l.Eu OH

1) JonebCIO,

2) F(41.5%)

Scheme 390

OH

0 (sq-137

13. Pheromone Ketones bakers’yeast

0

HO

Ho 0

Ih

193

OH

OH

(S)-137

la],zs t 6 t 0 (CHCI,) (92% e e ; 50% yield)

Scheme 391

R. 6-0x0-1-nonanol 138 (C9HI8O2) This is the rectal gland secretion of the fruit flies (Ducus occipitulis and (D. halfordiae). O’Shea and Kitching synthesized 138 by means of organotin chemistry (Scheme 392).512

( 61% )

Pb( OAc), ‘6’6

(79% )

> -

0

‘

1) B2H6 2) H z 0 2 , 0 H .

>

A

O

H

138

Scheme 392

S. Serricornin [(4S,6S,7S)-7-Hydroxy-4,6-dimethyl-3-nonanone] 139 (C I I H 2 2 0 2 )

Serricornin (139) is the female-produced sex pheromone of the cigarette beetle (Lasioderma s e r r i ~ o r n e ) . ~The ’ ~ .chemistry ~~~ and biology of 139 was extensively studied by Chuman et al.’’4-516Assignment of the absolute configuration to the three chiral centers of 139 was achieved as a result of the synthetic works to prepare several of the possible stereoisomers of 139 undertaken cooperatively by Chuman and MoriS5l4 Soon after the isolation of 139, Chuman et al. achieved a synthesis of a diastereomeric mixture of 139 (Scheme 393).’17 The synthetic product was bioactive at a dose of 1 ng. Ono et al. then developed a more efficient synthesis of the diastereomeric mixture of 139 (Scheme 394), which could be executed on a large scale for production of the pheromone traps.518 As the first step to clarify the absolute configuration of 139, (4RS,6R,7S)-139 was synthesized from (+)-tartaric acid (Scheme 395).’19 Conversion of (+)tartaric acid to A was a known process.520 After acetylation, the acetates of

194

The Synthesis of Insect Pheromones, 1979-1989

n

Elm&

>

4-40 OH

0

a diaslereomeric mixture 01 (+). 139

Scheme 393

a diaslereomeric mixlure 01 (*)-I39

Scheme 394

0

I)Ac,O I C5H5N

2) Nal 1 Me2C0

f55%1 . ,

7%

2) prep. GLC

2)AcOH (44%)

9

(4RS,6R,7S).139

(4R.6R.7S).139-acelale

(4S,6R.7S).139-acetate

(a],n-13.20 (hexane)

[a],n-t8 8' Ihexane)

Scheme 395

(4R,6R,7S)-139 and (4S,6R,7S)-139 were separable by preparative GLC. Neither of them, however, was identical to the acetate of the natural 139. The configuration of C-6 and C-7 was therefore thought to be either (6R,7R) or (6S,7S). Then (4RS,6R,7R)-139 was synthesized from ( 2 S , 3 S ) - ( +)-&methyl-

13. Pheromone Ketones

195

Scheme 396

aspartic acid (Scheme 396).52' The synthetic (4RS,6R,7R)-(+)-acetate of 139 was carefully compared (GLC and I3C NMR) with the (-)-acetate derived from the natural 139, and the absolute configuration at C-6 and C-7 of the natural 139 was concluded to be 6S,7S.52'The next, and the conclusive, work was the synthesis of (4S,6R,7R)-139 from D-glucose (Scheme 397).522Conversion of

n.BuU I THF-HMPA Ell (84%)

u

1) PPTSIEIOH 2) Ac20 I C,H5N

OEE

31HoCI2,CaCo3 8W. aq. MeCN

OAc (4S.6R.7R).139.acetale 46.75' (hexane)

-natural senicornin

Scheme 397

D-glucose to A was a known process in connection with the synthesis of a-multistriatin 234.523Because the synthetic (4S,6R,7R)-139-acetate was different from the acetate of the natural pheromone on the basis of GLC and "C NMR comparison, serricornin was concluded to be (4S,6S,7S)-139.522 Two different syntheses of (4S,6S,7S)-139, the natural pheromone itself, were reported in 1982. In the first synthesis, the key-step was the asymmetric alkylation of SAMP-hydrazone of diethyl ketone with iodide A (Scheme 398).524 Starting from (2R,3R)-P-methylaspartic acid, (4S,6S,7S)-139 was synthesized. Similarly, the antipode (4R,6R,7R)-139 was also prepared from (2S,3S)-Pmethylaspartic acid. Only the natural (4S,6S,7S)-139 was biologically active. The second synthesis started from cellulose (Scheme 399) to give (4S,6S,7S)-139 in a manner similar to that shown in Scheme 397.525

196

The Synthesis of Insect Pheromones, 1979-1989 1) HNO, 2) CH2N

HOzC&Co2H NHZ

OTHP

1) Me1 2) dil. HCI 3) AczO/ C6HsN

6R

0

R -AC.

R H (94% pure)

[aIDn-l6.7'

I&

pyrolysis

H

O

G

o

1) NaH, PhCH,CI DMSO 2) dil HCI.MeOH

0 7 (

A

A -

>

(45,65,75)-13#

Cellulose

2) T6OH / MeOH

M e o z C ~ C o z M e 3) Me,CO. TsOH) OTHP (81%)

,N , 1) TsCI / CH 2)Nal,K&0,/MezC0 3)TaOH IMeOH 4) CH,-C(OMe]Me. PPTS (54%)

HO&

1) LiAlH,

I

3) DHP. :SOH /EGO' (66.5%)

Similarly: H 0 , C l y C O Z H NH2

3

3) TsCl/ C6H6N (61%)

'

*

(4R.5R,7R)-139.acata1e [aIDn+19S0 (hexane)

(hexane)

e0

The acetate 01 nalural139 : [aJDa-17.70(hexane)

Scheme 398 MelCuli / € S O

Ph3P=CHZIE$O>

(64Yo)

Levoglucosenone

&

1) H2/ P I X

2) TsOH / CHCI,

>

1

I ) Ph,P, PhC0,H

Me,CuLi 1 Et,O

(77%)

P

S

ED,CN-NCO,EI

U

2)KOH / MeOH

s

U

3 ) *.PPTS ~z (-37%)

u

'

n.BuLi / THF-TMEDA OEE

6

R = H (45.65.75)-139 R = A c (4S,6S.?S)-13e-~mWa(Conminaied

OEE

2) Ac,O/ C,H,N 3) HgCI,, CaC03/aq MeCN

0

OR

With 8% 01 (4R.6SB7S)-139)[a),n-19 Cahbraled [a], -18 2'

67O(hexane)

Scheme 399

A synthesis of 139 by Mori and Watanabe (Scheme 400)526was based on the fact that 139 exists as an equilibrium mixture of the cyclic hemiacetal form and open-chain form.526*527 The starting material was methyl (R)-3-hydroxypentanoate (A), which was prepared by microbial &oxidation of pentanoic acid. Conversion of A to B was followed by Mitsunobu inversion at the secondary

13. Pheromone Ketones

-CozH

1) Candida Ngosa IF0 0750 2) melhylation

I ) LDA, Me1 OH A c o z M e A (93?be’e’)

2) DHP, PPTS 3)UAIH, 4) NaH, PhCH,CI

+e*++ (4S,6S,75)-139

( I : 2.8)

[ ~ ] ~ ’ ~ ~ - 1 8 . 2 ~ ( n h e x a[as n n acelate] s)

197

(4R,S,7S)-139

>

+OCHzPh B

7 1 (1 :o)

[ ~ ] ~ ~ ‘ . ~ ~ . 2 ~ ( n . h e[as x aacetate] ne)

Scheme 400

hydroxy group to give crystalline C. After recrystallization, C was further converted to iodide D. Alkylation of diethyl ketone with D yielded a diastereomeric mixture E. After deprotection, serricornin was readily separated from its (4R,6S,7S)-isomer, because the latter remained as the acyclic and polar form. Serricornin [(4S,6S,7S)-139] possesses only one axial methyl group in its hemiacetal form, while (4R,6S,7S)-139 must have two axial methyl groups upon cyclization. The latter, therefore, did not cyclize at all. The overall yield of serricornin by this route was 7.6% from A,”‘ Another synthesis of 139 by Sato and his co-workers was based on the diastereoselective addition of ethylmagnesium bromide to an optically active a-alkenyl-/3-trimethylsilyl-/3,y-unsaturatedcarbonyl compound B (Scheme 401).s28~529 Preparation of B was achieved by employing A, which in turn was obtained by the Sharpless epoxidation. Hydromagnesiation of C was followed by carbonation to give lactone D, which finally yielded serricornin acetate. Katsuki and Yamaguchi synthesized 139 by using their own asymmetric aldo1 and alkylation reactions (Scheme 402).497 Hoffmann’s synthesis of (4RS,6S,7S)-139 utilized yeast reduction of methyl tetrahydro-4-oxo-2H-thiopyran-3-carboxylate (A) to give optically active hydro,xy ester B with 98% d.e. and 83% e v e .This was purified by recrystallization of the (S)-a-phenylethylammonium salt of the corresponding acid C and used in the synthesis (Scheme 403).309*530 Baker and Devlin employed Masamune’s asymmetric aldol reaction with the

The Synthesis of Insect Pheromones, 1979-1989

198

Ti(OPr'), -OH

>

(+)-DET

&OH

I.BuM)H CH,CI,

Ph,CCI

A

.(

THF

cat. Cp,TiCI,/

2) CHC12C02H-Hz0 f84% I

(& (86% )

'lMg CO,Y] then HC02H ( 54% lrom C)

'

D

1) ElMgBr

THF 2) Ac, O / C,H,N

"a'"+

( 86% )

Cul, Me,S/THF

DMAP ( 8 9 % ) CH,CI,

0 Me1/ THF.HMPA

A M g B r

')

B

i.BuMgCI

LiN(SiMe,),

Me Si

A O C P h ,

EI,N

(> 95% e.e.)

( so %)

>

( 4s. 6S, 7 s )-l39-acatale

( 68% )

IaIDn-17.g0(hexane)

Scheme 401

/OMOM

(OMOM dil HCl

l)LDA/THF

heal

0

OH

OMOM 3)EtCHO

A

1) MOMCI. EtNPt2/CH2CI,

OMOM

2) LIAIH,lTHF

3)TsCI/ CSHSN

OMOM B

4) Nal /Me2C0 (79% )

..d

ELLi /E$O

Ac,O/C,H,N

OH

0

( 45.65.7s )-I39

OAC

0

( 45, 65, 7s )-139-aoetate

I:a)

-18 4' (hexane)

Scheme 402

boron enolate A in their synthesis of 139 (Scheme 404).53' Fujisawa et al. employed ester enolate Claisen rearrangement (A -+ B, Scheme 405) as the keystep in their synthesis of iodide C, an intermediate in the previous synthesis of 139.307Redlich et al. started from D-glucose, and prepared lactone B (Scheme 406), which had been converted to 139 by others.532 The same lactone B was also synthesized by Takano et al. starting from (S)-O-benzylgly~idol.~~~ Serebryakov and his co-workers employed (S)-3,7-dimethyl-l,6-octadieneto prepare the lactone B.534

13. Pheromone Ketones OH

nu

Baker's

1) (S).a-phenylelhylamine

( 71% )

OH

0

'

Raney-NI

MeOH

E (s95°/&e.e.)

( 73% )

2) ( n-Bu ),NF /WF

( 92% )

( 95% )

( 4RS. 6s.75 ).13%acelale

3) Ac,O /C5H5N

-18.5' ( MeOH )

[

( 18-21%)

Scheme 403

A 1) TsCIIC5H5N

\K/

( 4RS, 6s ,7S )-139

2) (n.Bu),NF

Scheme 404

h

-

(71%)

i

OH

6H 1) TsCl / C,H5N 2) Nal 3) t-BuMe,SiCI

1)TsCi/C5H5N

2)NaOH I Me0

'

b&i+

0

,i

1) b,Culi

HO+

2)0,

+/+-3) LIAIH,

OH

I

(45.6s. 7S).139

C

Scheme 405

6H

199

200

-

The Synthesis of Insect Pheromones, 1979-1989

D-Glucose

1) Oxidn

+

i)BO%AsOH 2) NalO,/aqEtOH

'

-B0

OHC

DMSO I 1) HCI aq 2) NalO,

'

HdRaney Ni

MeOH (76%)

0

Of-

II

*co,,

(76%)

Schemes 401,

e - + (4S,65,75)-139

Scheme 406

Two stereoselective syntheses of ( f)-serricornin (139) are worthy of note. First, Bartlett et al. employed stereocontrolled iodolactonization reaction (A B) to prepare the acetate of (f)-139 (Scheme 407).535Pilli and Murta synthesized ( f )-139 by using Heathcock's syn-selective aldol reaction (Scheme 408).536An interesting feature of this work is the preparation of the lactone A ( > 98% pure by capillary GC) with proper stereochemistry by equilibration at

-+

c-1.

Extensive biological works were done concerning 139.5143537On1Y (4S,6S,7S)-139 showed pheromone activity. (4S,bS,7R)-Isomer of serricornin was inhibitory against the action of (4S,6S,7S)-139.538 Pheromone activity of the stereoisomers of 139 was studied carefully in order to develop pheromone traps. 539-54

'

14. ACIDS AND ESTERS AS PHEROMONES Perhaps the best-known compound in this group of pheromones is (E)-g-oxo2-decenoic acid, the queen substance of the honeybee. Compounds in this group will be discussed according to the increasing order of the carbon chain length.

14. Acids and Esters as Pheromones

Me,SiOTI CH,CI, (91%)

'

ono

CsOAc

1)NaOWaqMeOH

DMF (51%)

2) MsCUEbN CH,CI,

201

>

(91%)

(4R*,6R*,7R*)-IlB

acetale

Scheme 407 1) L D M H F , -78OC

2) ECHO

'

OAc 0

3) Ac20/DMAP.E&N

1) Ad)H/aqTHF 2) NsBH,/MeOH

--VH0 1

3)NelO,/aqElOH

CH,CI, (80%)

?Ac

(76%) ($-acetoxy kelone

0 Me

II I

EIMgBr/EbO

(EO),PCHCO,EI

(87%) (61%)

(65%)

A

(4R*,SR*,7R*).139

Scheme 408

A. (2)-3-Dodecenyl (E)-2-Butenoate 140 (C ,6H2802) This is the female-produced sex pheromone of the sweet potato weevil (Cyfas

formicarius elegantulus). Acylation of (Z)-3-dodecen-1-01 with (E)-2-butenoyl chloride provided 140 (Scheme 409).542

202

The Synthesis of Insect Pheromones, 1979-1989

140

Scheme 409

B. Methyl 3-Isopropylpentanoate 141 (C9H This ester was identified from ants: the red wood ant (Formica rufu) and the small forest ant (Formica polyclen~).'~' In the case of the latter, 141 was identified from the heads of workers, as well as from heads of old queens.544 In laboratory bioassays, 141 showed a strong aggregation-inhibiting effect.544Both (R)- and (S)-141 were synthesized by Tanida and Mori, starting from the enantiomers of carvone (Scheme 410).545An asymmetric synthesis of (S)-141 was

Similarty:

'63 A

(S)-(+)cawone

Me0z9 h (S).141

[a],2'+2.0k0.15°

(€(OH)

Scheme 410

reported by Enders and R e n d e n b a ~ h . 'The ~ ~ key-step was the asymmetric Michael addition of lithiated propanal-SAMP-hydrazone to methyl (E)-2-pentenoate (Scheme 41 l).546

14. Acids and Esters as Pheromones

':]a(

203

t2.07' (EIOH)

Scheme 411

C. Sitophilate [I-Ethylpropyl (2S,3R)-2-Methyl-3-hydroxypentanoate]

142 (clOH22O3)

The male-produced aggregation pheromone of the granary weevil (Situphilus grunurius) was isolated by Burkholder et al. and identified as 142."' They also accomplished the synthesis of (*)-142(Scheme 412).547

Scheme 412

Chong synthesized both the enantiomers of 142 by the Sharpless epoxidation and organocopper chemistry (Scheme 413).548Mori and Ishikura also synthesized the enantiomers of 142, starting from the pure enantiomers of methyl 3-hydroxypentanoate (A) (Scheme 414).549 The key-steps of this synthesis were the dianion alkylation (A B) and the Mitsunobu inversion (C -+ D). Bioassay of the synthetic samples revealed (2S,3R)-142 to be the natural pheromone.550 +

D. (E)-9-Hydroxy-2-decenoic Acid 143 (C

*03)

Queen honeybees produce (E)-9-hydroxy-2-decenoic acid (143) in their mandibular glands as a component of the swarm-setting pheromone. Both the en-

204

The Synthesis of Insect Pheromones, 1979-1989 1) NaOH/aaTHF

1) li(OPi).,(+).DIPT

3) Rocrjsklltzalion (52%)

(69%)

(2S,3R)-142 -3.1' (CHCI,)

Similarly:

Scheme 413 1) LDA,Mel/THF-HMPA

2)

I +PI

.' I

3) LiOH/aq THF

(42%)

I ) (COCU,/C,H,

I

imidazoleiDMF

2)

+'OZH

r)-OH

B

=

DMAP/C5H5N.CH,CI,

3)HF/aqMeCN

>

(67%)

+02= C

[ a ] ~ " -3 9' (CHCIJ

Similarly:

OH &CO,Me

(ZR 35)-I42

[aJD" 14.1' (CHCI,)

Scheme 414

antiomers of 143 were prepared from the enantiomers of propylene oxide (Scheme 415).55'The more bioactive isomer was (R)-143.551

E. (E)-9-Oxo-2-decenoic Acid 144 (C,,H,,O,) This keto acid 144 is known as the Queen substance of the honeybee and inhibits ovary development in workers. It influences worker bee behavior by inhibiting Queen rearing.

14. Acids and Esters as Pheromones

205

0 PCC/CH,CI,

h

(96%)

OAc M

c

o

*

M

H

O

THF [ 70%)

(R)-143

[ulon -5.4’ (EIOH)

4

Similarly:

1 I

C

NaH,(MeO],PCH,CO,Me

OH -CO,H

NaOH sqMeOH (68%)

e

OAc

OH -CO,H

$ - + +

(S).143

[alDn+5.2O(EIOH)

Scheme 415

Fujisawa et al. developed a synthesis of 144, employing as the key-step the reaction of P-vinyl-/3-propiolactone (A) with a Grignard reagent B in the presence of cuprous iodide (Scheme 416).”* Ogura et al. improved the Trost syn-

V

B

Y

-7806‘

-

heal

0

(37%)

144

(46%)

Scheme 416

thesis (Scheme 21 1, Ref. 1) of 144 by using their novel method for preparation of 2-(methylthio)alkanoic ester (Scheme 417).5s3

+

MsCVC,H,N EtOH.heat ‘Co”KI)

& O -H

L

O

H

>

L

(37%)

NaOEVElOH

0

>

k

C

0

2

C0,EI

COMe

(40%) I) NalO,

2)tduene

’

E

0 A

C

0

,

E

I

l

1.4eq NaOEVEtOH

MeSSO,Me (98%)

OH‘>

> SMe

0

CaCO,.heat

\

144

(Trosl!

Scheme 417

CO,H

O

M

s

206

The Synthesis of Insect Pheromones, 1979-1989

Chadha and co-workers prepared 144 starting from aleuritic acid, a readily accessible component of shellac (Scheme 418).554The acid A was cleaved with sodium periodate to give B, which was converted to the key keto aldehyde C.

Diethyl 3-oxoglutarate was the starting material of Naoshima’s efficient synthesis of 144 (Scheme 419).467VilliCras et al. found that liquid-liquid hetero-

0

0 (61%)

(80%)

144

(375% overall yield)

Scheme 419

geneous media of low basicity such as potassium carbonate solution allow the Wittig-Homer reaction of fragile aldehydes in good yield, and they applied this method to the synthesis of 144 (Scheme 420).555VilliCras’s synthesis of 144 was quite efficient (Scheme 421).556 0

II

(E0),PCHzCO2Me

20°C

lh

KOH (8 I%)

Scheme 420

144

14. Acids and Esters as Pheromones

n

1) MgKHF

0x/Lc, 0

207

dilHCl

2, &CH(OEI),

/

B)LiEr,CuEr

L

C

H

O

OEt

0

II

0

(EtO),PCH,CO,EI

0

KOH

144 (58 4% overall yield)

Scheme 421

A slight modification of Barbier’s synthesis (Scheme 208, Ref. I ) was reported by Villemin (Scheme 422), in which reagents supported on alumina were

0

II

L

C

H

O

0

>- I ) (EO),PCHZCO2El KF-AI,O, 2) KOH

144

Scheme 422

employed.557 Ferroud et al. synthesized 144 (Scheme 423) by using

NaCH(SO,Ph),

Pd(dpp), TUF

....

-

SO Ph P h S O z L o H

+

SO Ph P h S 0 2 L O H

2) NaH

>

(70%)

3) Na-Hg (69%)

l)AcOH/eqTHF

(60%)

144

Scheme 423

bis(phenylsu1fonyl)methane as the pivotal building A synthesis of 144 was achieved by a three-carbon elongation method (Scheme 424).559This synthesis, however, is lengthy and inefficient. Bestmann et al. reported a unique synthesis of 144 by chain-lengthening of a Grignard reagent derived from A with ketenylidenetriphenylphosphorane (B) (Scheme 425).560Another synthesis of 144 was reported, in which 7-oxooctanal

The Synthesis of Insect Pheromones, 1979-1989

208

1) I4dPd.C

(EO),~CHCO,EI

I

L

C

H

CH,CO,Et

O

C02EI

>

NaH/C,H,

2) NaOH / aqMeOH

>-3) Jones CO,

Scheme 424

>

NaNH,

Ph,PCH,CO,Me

Ph,P=C=C=O

B

loluene

(.NaOMe)

(ew

TaOH

B~-CHO

tduene

1 ) MglrHF

>

0 0 3 A

(55%)

0

*

NaHCOJ

~ T H F heat

L

C

H

a

ZZ?

(60%)

2

dlHCl Me,co’ (92%)

O

was employed as the key-inte~mediate.’~’Webster and Prestwich prepared carrier-free tritium labeled Queenbee pheromone 144.562 Ishibashi’s application of sulfur chemistry resulted in a new synthesis of 144 (Scheme 426).563Suzuki’s synthesis of 144 was based on his new synthetic

14. Acids and Esters as Pheromones

1) Nel0,laq MeOH 2) NaHCO@Amw, heat

3)on

(273%)

209

0

2

-

\d C0,H

144

Scheme 426

method for (E)-a$-unsaturated esters by the highly chemoselective reaction of B-iodo-9-BBN-ethoxyethylene adduct with aldehydes (Scheme 427).564

Scheme 427

F. Methyl (2E,42)-2,4-Decadienoate145 (C, IH1802) This is a pheromone component of the forest pest six-spined spruce bark beetle (Pityogenes chalcogruphus) together with chalcogran 238. Strong synergism was observed between 145 and chalcogran 238 in attracting P. chafcogruphus. The mixture caught 34 times more beetles than chalcogran alone, while 145 had no activity at References to all of the existing 19 different syntheses of 145 are cited in Baeckstrom's paper.566 Baeckstrom et al. prepared 145 by transesterification of the commercially available ethyl (2E,42)-2,4-decadienoate (76% purity) with sodium methoxide in Crude 145 was

210

The Synthesis of Insect Pheromones, 1979-1989

further purified by removing the (2E,4E)-isomer as urea inclusion complex. The purified (2E,4Z)-145 was > 99% pure (Scheme 428).566 1) NaOMelMeOH 2) Urea i w l u ~ i o n

-

P

-CO*Et

3) IilValton 01 the complex 4) chromatog of the molher liquior

Impure

\

C0,Me

145 >99% pure

(76% purity)

Scheme 428

G. (2)-and (E)J-Undecenoic Acid 146 (C, ,H2,,02) The female-produced sex pheromone of the varied carpet beetle (Anrhrenus verbasci) was identified by Kuwahara and Nakamura as an 85 : 15 mixture of (2)5-undecenoic acid (146) and its E - i ~ o m e r . ’They ~ ~ synthesized a 75 : 25 mixture of (Z)- and (E)-146, starting from 5-acetoxypentanal (Scheme 429).567Harada 1)

onc -OAc

PhP ,-

2) OH’

>

C02H 146

3)Jones CrO,

Z : E = 75 : 25

Scheme 429

and Mori synthesized an 82 : 18 mixture of (2)-and (E)-146 in a simple manner starting from dihydropyran (Scheme 430).568

Scheme 430

H. Methyl (2)-5Tetradecenoate 147 (C ,5H2802) The female-produced sex pheromone of the soybean beetle (Anomala rufocuprea) was identified by Tamaki et al. as 147.569They synthesized it by the Wittig reaction followed by chromatographic purification (Scheme 43 l)?’

14. Acids and Esters as Pheromones

0 1

,NaHCO,

0 toluene

Br(CH,),CO,Me

211

1) Ph,P=CH(CH,),Me

>

DMSO (21%)

OHC(CH,).,CO,Me

/

2) chromatog. (SD2-AgNO3)

(6W)

Scheme 431

I. Megatomoic Acid [(3E,SZ)-3,5-TetradecadienoicAcid] 148

(c14H2402)

This is the pheromone of the black carpet beetle (Aftagenusmegatornu). Tsuboi et al. prepared 148 stereoselectively by the rearrangement of an allenic ester A to (2E,4Z)-dienic ester B (Scheme 432).570

OH

>

I

>

Me(CH,),C-C=CCH,CO,El H H

heat, H+

Me(CH2),CHCi CH

A'201 BOOC (88%)

A

(85%)

SMe H H H Me(CH2),C-C-C-CC0,El H

B

(97% pure)

H H

H H H Me(CH,),C-C-C-CCH,Er H

')

2) PBr,

1) UiHS0,Me

2) H202.AcOH

(75%)

(46%)

H

/SOMe Me(CH,),C=C-C=CCHzCH H

\so,Me

1)HCUMeOH 2)O.BM-KOH (27%)

Scheme 432

'

b:C=C'

WCHJ,/

\

148 (74% pure]

H

/

212

The Synthesis of Insect Pheromones, 1979-1989

J. (32,52)-3,5-TetradeeadienoicAcid 149 (C 14H2402)

Arragenus elongatulus employs this acid 149 as a pheromone component. DeJarlais and Emken reported a synthesis of 149 by employing classical acetylenic chemistry followed by hydroboration-protonolysis (Scheme 433).57'

Me(CH2),C 9C-C fC(CH,)20H

(df,'.

RCO,H

(82%)

>

H H H H Me(CH,),C=C.C=C(CH,),OH

149

Scheme 433

Rossi et al. prepared (32,52)-3,5-tetradecadienylacetate, which can be a useful precursor for the synthesis of 149.17*

K. Methyl (R,E)-2,4,5-Tetradecatrienoate150 (C,5H2402) This is the male-produced pheromone of the dried bean beetle (Acanthoscelides obtectus). Mori's synthesis of both (R)-and (S)-150was published in full detail (summarized in Scheme 434).572Two additional syntheses of optically active 150 have been reported. Oehlschlager and Czyzewska applied the Sharpless asymmetric epoxidation to the synthesis of 150 (Scheme 435).573Reaction of dioctylmagnesium cuprate with alkenyl epoxy alcohol A gave dihydroxyallenes B and C in a ratio of 9 8 : 2 when the reaction was carried out in the presence of dimethyl sulfide. Their synthetic (R)-150,however, was of only 49% e.e. based on the maximum [a],, value reported for 150.572Fujisawa et al. synthesized 150 by the reaction of propargyl alcohol A with ally1 Grignard reagent using l-chloro-2-methyl-N,N-tetramethylenepropenylamineto give (S)-B via a

14. Acids and Esters as Pheromones

(88%)

(R,E)-150

lnlon -162' (hexane)

Cl.NaNfal150: [aJD -128' (hexane)

Scheme 434

WDET

Wph,

/OH

I.BuOOH (43%)

88

H

'

OH

ether, BO'C.

H A ('high e.e.')

(57%)

2

B

C

0

Me(CHz),

H= )%;

CHO

(MeO)2PiHC02Me II

ElzO

(41%)

IMe(CH,),J,CuMgBr,MezS

>

Scheme 435

1.6h

213

The Synthesis of Insect Pheromones, 1979-1989

214

1 )PCC/CH,CI,

(QG%j

co2Me

H

syn-type of S,2' reaction (Scheme 436).574 They obtained both (R)-and (S)-C, which were previously converted by Mori et al. to the enantiomers of 150.572 Five syntheses of ($)-150 were reported in the period between 1979 and 1989. Franck-Neumann and Brion synthesized (+)-150 via allenemanganese complexes (Scheme 437).575 Reduction of y-bromo-a-acetylenic acetal A to

Fe(m' (92%)

H > Me(CH2),CH-CICHCICC02h4a H

(&)-150

Scheme 437

14. Acids and Esters as Pheromones

215

a-allenic acetal B with chromous ion was used by Ledoussal et al. in their synthesis of (f)-150 (Scheme 438).576Lang et al. synthesized (f)-150by the Me(CHZ)~CHBr~CCH(OE1)2 A (CO2H)z aqEIOH

CrCtflHF-HMPA AcOH (47%)

> Me(CH,),CH=C-CHCHO

H

H

> Me(CH,),C=C.CCH(OEI),

Ph,P=CHCO,Me

(66% lrom 8)

E

>

H Me(CH,),CH=C=CHC=CCO,Me (*)-150

Scheme 438

Wittig reaction (Scheme 439).577In a synthesis of (f)-150(Scheme 440), Bloch Me(CH2),COCI

+

Ph,P'CH2C-CC0,Me H B i H

EkN,CH,CI, (21%)

> Me(CH,),kC-CC-fiCO,Me HH (f)-150

Scheme 439

(64%)

A

Scheme 440

et al. employed extrusion of sulfur dioxide from A as the ..;~-step.~'' As shown in Scheme 441, Yamaguchi and his co-workers reduced propargylic lactone A with samarium iodide and zero-valent palladium in the presence of 2,4-dimethyl-3-pentanol to produce allenic ester B after m e t h y l a t i ~ n . ~ ~ ~

Scheme 441

216

The Synthesis of Insect Pheromones, 1979-1989

15. PHEROMONE LACTONES Many lactones have been isolated as insect pheromones. In this section, y- and &lactones with alkyl side chain will be discussed in order of the increasing length of the main carbon chain. Macrolides will then be discussed. Terpenoidal lactones are discussed in Section 18.

A. 4-Hexanolide 151 (C6H,002) This y-lactone 151 was isolated as a pheromone component of the dermestid beetle (Trogoderma glabrum). The khapra beetle (Trogoderma granariurn) was reported to respond to (R)-lSl,but to neither (S)-151nor ( *)-151.s80Bioassay of both the enantiomers of 151 as prepared by Mori"' was found to be inactive against T. glabrum when assayed by Levinson.s82 Neither of the enantiomers of 151 was synergistic to the action of (R,Z)-trogodermal (114),the major pheromone of T. glabrum. Optical resolution of (f)-151on a column of cellulose triacetate (crystallographic form I) was reported, which enabled the resolution in a preparative scale.583Serebryakov and his co-workers prepared (+)-151as shown in Scheme 442.s84 ECHO

1) +MgC'

EtCH(OAc)CH,CH-CH,

2)Ac2O/Et,N.Dh4AP (67%)

EICH(OAc)(CH,),CO,H

(51%)

1)KOWMeOH 2)H' (86%)

(*).is1

Scheme 442

(1) Syntheses Starting from Chiral Building Blocks

Five syntheses of optically active 151 were achieved starting from optically active natural products. Serebryakov prepared (R)-151from (S)-glycerol acetonide (Scheme 443).585Kang and Shin began with (R)-glyceraldehyde acetonide to prepare (R)-151(Scheme 444)."' L-( +)-Tartaric acid was also converted to (R)-151in two different manners (Schemes 445 and 446).s87.588Gurjar and Patil published a lengthy synthesis of (R)-151from D-glucose (Scheme 447).s89

15. Pheromone Lactones

Scheme 443

3)PDC (45%)

(55%)

(65%)

Scheme 445

[a), +53'(MeOH)

217

218

The Synthesis of Insect Pheromones, 1979-1989

3;

OCH Ph OH

CO,H

- =

MsO&'OM8

MsCVESN CH2CIZ (96%)

(80%)

(60%)

Nal ElCOMe

OM3

(74%)

(74%)

A

'

Scheme 446

D.GIu m se

""k

l)E,HflHF

P)H,O,.NaOAc 3)NaH,PhCH20r 4)HCI.MeOH

(@W

l)OFl.El~O,MCPOA CH,CI,

>

%z$o

l)H,SO,/aqMeOH

(n-0~)~SnCl.h~

2)MsCI/C5H5N

NaBH(,/MeOH

3)Nal/EffiOMe

>

p h c H z o ~ O M e l)NaH.CSz.Mel P)(n-Bu),SnH AlBNnoluene OH 168%) . .

>

>

PhCH'o%OMe

2)HJPd-C (58%)

Al0N/Ioluene (47%)

lal, +=OWOH)

Scheme 447

(2) Syntheses Based on Chemical Asymmetric Reactions Three chemical asymmetric syntheses of 151 have been reported to date. Vigneron and Bloy employed lithium aluminum hydride modified with N-methylephedrine and 3,5-dimethylphenol to reduce a-acetylenic ketone A to optically active propargylic alcohol B (Scheme 448).590Because acid C was crystalline, pure (R)-151could be obtained.590Midland and Tramontano reduced acetylenic keto ester A (Scheme 449) with B-3-pinanyl-9-BBN to give B, which was converted to (R)-151.59' Chemoselective alkylation of formyl ester A with dialkylzinc using N,N-dibutylnorephednne enabled Soai et al. to prepare (S)-151 of 92% e.e. (Scheme 450).592

15. Pheromone Lactones

219

OH Cm.p. UOC

(R)-l51

lalo= t 5 1 .SO(MeOH)

Scheme 448

Scheme 449

(3) Syntheses Based on Biochemical Asymmetric Reactions Six syntheses of 151 used biochemical asymmetric processes. Fuganti and his co-workers employed A (Scheme 451) as the starting material, which could be prepared by fermentation of cinnamaldehyde with baker's yeast and glucose.593 Naoshima et al. reduced keto ester A (Scheme 452) with baker's yeast to give

220

The Synthesis of Insect Pheromones, 1979-1989

Scheme 451

4)MeOH.H' (61%)

l)NaOH/MeOH

Scheme 452

(R)-151.594Mori et al. employed the enantiomers of 3-hydroxypentanoic esters A and B to prepare 151 (Scheme 453).58'The (R)-enantiomer A was commercially available and could be purified to an optically pure state by recrystallization of the corresponding 3,5-dinitrobenzoate. The (S)-enantiomer B was obtained by yeast reduction of C.58'Kozikowski et al. reduced a phenylsulfone A with baker's yeast to give B, which finally afforded (S)-151 of 60% e.e. (Scheme 454).s9s Fujisawa and his co-workers reduced /3-keto sulfone A with baker's yeast to give B, which was converted to (R)-151 (Scheme 455).596 Blanco et al. achieved the kinetic optical resolution of ( k ) - l S l to give (R)-151 of 75% e.e. (Scheme 456).597 B. cis-2-Methyl-5-hexanolide 152 (C7HI2O2)

This was isolated as the major volatile component of the pheromonal blend of the carpenter bee (Xylocopa hirsurissima). Five new syntheses of (+)-152 have been reported since 1979. Bacardit and Moreno-Mafias converted dehydroacetic acid (A) to (f)-152 (Scheme

15. Pheromone Lactones OTHP \jCOZMe OH l)DHP.TsOHICH2C4 l)TsCVCIH6N

AoH

Z)UAIH,/E(20 (86%)

A

(-1W.e.)

2)NaCWDMF

(76%)

221

’

(Rb1.51

(77.5%) [a2],o’.

+53.1‘(MeOH)

Similarly:

Scheme 453

OH

0

OH

l)OdCHzClz

A

HMPA

Scheme 454

Raney Ni

(79%)

>

H~-

OH

Ag,CO, celite (80%)

’

(R)-151

[a],n +SO.S’(MeOH)

Scheme 455

2)Jones CO, (78%)

’

222

The Synthesis of Insect Pheromones, 1979-1989

Scheme 456

OH0

OH

OH

9'1

(fj.152

Scheme 457

457).598*599 The first and key step of Backvall's synthesis of (&)-152 was the stereocontrolled 1,4-addition to a conjugated diene catalyzed by palladium (Scheme 458).600 Narasaka and Ukaji synthesized (i-)-152 by a highly stereo1) PhS0,,N02

HnH ,

PhSO,

PhSO

DHP.Ts0H CH,CI, (80%)

H

,

H

p

1 )NaOH.KMn0,1H20

3)OH' 2 1 ~ ~ 1

4'H' 158%1

(f).lS?

(>93%

CIS)

Scheme 458

selective alkylation reaction of an ester enolate generated from r-butyl S h y droxyhexanoate (Scheme 459).60'A synthesis of (+)-152 by Ibuka et al. employed organocopper-Lewis acid-mediated 1,3-chirality transfer of acyclic y,6-

15. Pheromone Lsctones

-

223

1)%q LiNElJfHF.HMPA

OH

C0,Bu’

-78

-lOo0C

(71%) (95:5)

CF,CO,H

Scheme 459

&cozM OMS

Me,Cu(CN)Li,*BF, (96%)

&COzMe (2S’,5R’)

Scheme 460

$g&PMeCN

no (f)-157.

dioxygcnated (E)-a,P-unsaturated ester (Scheme 460).602Another synthesis of (f)-152 utilized organosilicon chemistry, especially stereoselective alkylation of A to B (Scheme 461).603

Four syntheses of optically active 152 have been published based on the chiral building block approach. Mori and Senda synthesized both (2R,SS)-152 and (2S,5R)-152, starting from the enantiomers of methyl 3-hydroxy-2-methylpropanoate (A) and ethyl (S)-lactate (B) (Scheme 462).604This approach enabled them to prepare enantiomerically pure 152. Gerth and Giese synthesized (2RS,5S)-152 and (2RS,5R)-152 by using chiral radical precursors to achieve radical-mediated C-C bond formation (Scheme 463).605Brandange et al. prepared (2S,SR)-152 in a concise manner from methyl (R)-3-hydroxybutanoate A (Scheme 464).606Bernardi and Ghiringhelli synthesized the enantiomers of 152 starting from a dithiane alcohol A (Scheme 465).607A synthesis of (2R,5R)-152,

224

The Synthesis of Insect Pheromones, 1979-1989 1lDHP.TsOH/THF

mp 49 :M'C

[aloQ-9l.O0(CHCI~

Similarly:

Scheme 462

0CH2Ph

&I

JC0,Me Bu3SnCI NaBHJEDH

?H,Ph

>

/VyCopMe > 1) HJPd-C 2 L m 15

(2RS,SS)-151 mp 5 5 ' ~

hv ...

(35%)

l)TsOH/MeOH 2)TsCI/C5H,N

r , o ~ c o , M e

NaBH./EDH h; (45%)

DHP.TsOH CH,CI,

(62%)

(93%)

mp 5 3 ' ~

Scheme 463 OH

0

Scheme 464

OAc

15. Pheromone Lactones

.sublirnalion .

225

(25,5R)-162 mp 49-5OoC

[a],2o+s8.2°(CHC13)

mp 4 8 - 4 9 ' ~

lalorn47.6°(CHC13)

Scheme 465

a stereoisomer of the pheromone, was reported by Hanessian et al. starting from a sugar.608 Only one asymmetric synthesis of 152 has been reported by Katsuki and Yamaguchi (Scheme 466).497Their synthesis was a combination of yeast reduction and alkylation of the amide enolate derived from C with B.

bakeri yeast

0

&COzEt

>

OH -CO2Et

>-

Me,SiCH,CH,OCH,CI (SEMCI) EtNPrl,/-CH,CI, .

A (95%e.e.)

1) LUiH. I THF 2) TsCl / C,H,N 3) Nai / Me,CO (78%)

'

(80%)

1) LDA I THF

FSEM M

I

B

OMOM

OSEM &CO,Ei

2) B. -78OC

1) dil.HCI

heal

(76%)

2) recryal'n.

Scheme 466

C

226

The Synthesis of Insect Pheromones, 1979-1989

C. (22,62)-2,6-Nonadien-4-olide 153 (C9HI2O2) This lactone, together with 0-phenylethyl alcohol, was isolated by Kuwahara as the possible male-produced sex pheromone of a pyralid moth (Aphomia guh i s ) . He synthesized (f)-153 (Scheme 467), but it was behaviorally inactive H H EIC=CCH,CHO

BfMgCsCCH,OTHP THF

H H EIC=CCH,CHCECCH,OH

>

1) Ac20 / C,H,N

H H EIC=CCH,CHC.CCH,OTHP

21 TsOH / MeOH

I

MnO, / Me,CO

>

I

Jones CrO,

H H

EIC=CCH,CHC=CCHO

I

OAc

OAc

1) H, / Llndlaf Pd / MeOH

H H ElC.CCH,CHC=CCO,H

2) TsOH , MeOH

I

OAc

>

4

0 (+)-153

Scheme 467

against the female moth.609Miyashita and Mori synthesized the enantiomers of 153 by resolving an intermediate (Scheme 468).6'0 The synthetic enantiomers of 153, however, were biologically Further studies are necessary to clarify this matter.

3) NaOH (93%)

-

(R).153 lalo'' -162O(GHCI,)

(74%)

Similarly

OH

(962 Y a . e . )

[a]:'+

Scheme 468

(S)-l53 161°(CHCI,)

(96 5% e e )

15. Pheromone Lactones

227

D. Invictolide [(3R,5R,6S,l'R)-3,5-Dimethyl-6-(l'-methylbutyl)tetrahydro-2H-pyran-2-oneI 154 (C12H2202) Invictolide (154)is one of the three lactones (154,155, and 210) isolated from the red imported fire ant (Solenopsis invicra) as the Queen recognition pheromone,61 1.612 Rocca et al. synthesized (f)-154as proof of their proposed structure (Scheme 469).6'2Their synthesis was nonselective, and they had to separate the unwanted isomers two times.

0

0 1) UINH.

0

(&)-A

"

0

-& MCPBA

(*).I54

=

0 7 4'

-[+&I

\._.",

1) LDA I THF 2) Me1 I HMPA

o +

3)HPLCsepn.

Scheme 469

Four additional syntheses of (f)-154 have been reported. Hoye et al. devised an interesting synthesis of (f)-154(Scheme 470).6'3They stereoselectively methylated spiro-dilactone ( f ) - B , which was prepared from A, to give ( f)-C.614After hydrolysis, (&-)-Cgave (5)-D. Its lithium-ammonia reduction was followed by thermodynamically controlled lactonization to give (*)-E[( *)E: its isomer = 14.6 : l].6'3 Further conversion (as shown in the Scheme) furnished (f)-154.Schreiber and Wang synthesized (f)-154by stereoselective formation of a spiroacetal ( f ) - B from (+)-A (Scheme 471).6'5That spiroacetalization established the three chiral centers out of four in the invictolide molecule. Y. Yamamoto et al. employed the Lewis acid-mediated reaction of (+)-A with an allyltin B as the key-step (Scheme 472) and obtained (+)-154as a minor Stereoselective cyclization of enyne (*)-A mediated by zirconocene (Scheme 473) yielded (*)-ketone B, which was an intermediate in a previous synthesis of ( f)-154.6'7

228

The Synthesis of Insect Pheromones, 1979-1989

Scheme 470

-c

15. Pheromone Lactones

1) BF,*E$O, H,O

"'.&

+

I

" 4 . k

2) H, / P&C

229

0

0

(7040%)

73

(

:

(*).I54

24

Scheme 472

(*)-A

I

1) CpgrCI, / 2BuLi

1) (n-Bu),NF / THF

2) dl HzSO,

2) 1.BuCOCI DMAP , ESN, CH,CIz (70%)

>

3)SO, chromalog. 37%

57%

(COCI), , DMSO

5% CUCN I EbO

2) H20z / O H

EgN / CH,CI,

(78%)

(74%)

-

-

(61%)

(Scheme 469) (*).154

Scheme 473

Five syntheses of optically active 154 have been published. Ziegler et al. synthesized unnatural (+)-154(Scheme 474),6'8,6'9starting from (R)-3-methyl4 - b ~ t a n o l i d e . ~The ~ ' key Claisen rearrangement (A B + C) was highly stereoselective after equilibration at C-2 to give C of 95% d.e. and > 99% e.e. After a lengthy sequence of reactions, C yielded (+)-154.Zieglaer et al. also prepared (f)-154by the same route, starting from (f)-3-methyI-4-b~tanolide~'~ and found (f)-154to be bioactive, while (+)-154was inactive. Shortly afterwards, Mori and Nakazono prepared both the enantiomers of 15462'and (-)-154was indeed bioactive.622 In this synthesis, the four chiral centers of 154 were constructed by means of the Sharpless asymmetric epoxidation of allylic alcohol A, diastereoselective methylation of 0-hydroxy ester

+

The Synthesis of Insect Pheromones, 1979-1989

230

1) MeU / EhO 2) H20,-AcOH / THF

1)

3) AC201DMAP , EgN / CH,CI, _7 4) LIAIH, / Eb0

EgOBF,

0 '

Q O E I OE1 A

EtOH

5) Me,C(OMe),, TsOH

2) KOBU '/ bBUOH-E$O (94%)

(=w

C

'

+

4) MeOH / HCI (44%)

1) MeLi / EbO

Pd(Ph,P),

Ph,P/THF

(84%)

2) H,O,-AcOH / THF 3) AC,O, DMAP , E$N> 4) UAIH, /E$O

(46%)

i)o,,~e~s

H

o

2) (Me0)3CH,TsOH'

(32%)

OM

e

1) n&L i /THF 2) PhOCSCl / THF 3) (mBU) SnH ,AIB taluen~,heal 4) 0 . / EtOH 5) T ~ /CH,CI~ H

'

(33%)

(3S,5S,6R,l'S)-154 [a], n . 4 ' (CDCI,)

Scheme 474

B, and the Evans asymmetric alkylation with alkylating agent C (Scheme 475).62'Instead of asymmetric epoxidation, enzymatic resolution of the N-chloroacetylamino acid A (Scheme 476) was also employed for the preparation of diol D,the key-intermediate in the synthesis shown in Scheme 475.623 Wakamatsu et al. started from levoglucosan and obtained a 74 : 26 mixture of (-)-154and its 3s-isomer (Scheme 477).624Balestra and Kallmerten synthesized ( -)-154 by using diastereoselective [2 -31 Wittig rearrangement of a tertiary a-lithio ether as the key reaction (Scheme 478).625 E. (2Z,42,6E)-2,4,6-Decatrien-S-oIide [(E)-6-(1-Pentenyl)-2H-pyran2-oneI 155 (C,0H,202) Together with 154, this is a component of the Queen recognition pheromone for Solenopsis invicta, which attracts worker ants and causes them to move

--15. Pheromone Lactunes

Pd-BaSO

H,/

, quinoline

C,H,

THF (8496)

(8%)

0

0

-

&OH

OH

-2OOC (56%)

0

3eq Mepl

(37%)

+CO,Me

(52%)

OH

(79%)

Mel/HMPq (49%)

'

penme 0.4 eq n-Bub

OH D

(86%)

1) DHP, PPTS 2) LAIH, / €50-

+C02Me

3) TsCl/ CH ,N , 4) Nai , NaHC03

OH

B

DMF (32%)

Scheme 415

A)'cHCI

1) CICH,COCI NaOH aq

1) KCN / NH,CI NH, aq

2)concHCI NH2

amino acylase Cock. pH7.l

LLAIH, / Eb0

> Din Scheme 475

Scheme 416

OH

(80.4% e.s.)

LDA / THF

4C% aq E O H

0

2'

D-DIPT

A

(lac% e.e.1

1) NaCN

Ti(OPi),

231

2) reciysl'n hom Me,CO

NHCCCH,CI A

232

The Synthesis of Insect Pheromones, 1979-1989

[alDP-760(CHCI,)

Scheme 477

1) %ern oxid'n. 2) MekCMgBr

a

(nW&

A 3) UAIH, 4) (n -BU),SnCH,CI (ca.80%)

' -

-

OBOM

n -BuU THF (57%)

HZ/ Rh(NBD)(Diphos)BF,

CH,CI,

(84%)

-

OBOM

OH

1) H, / Pd-C

OH

OBOM

2) Ag,CO,

CeH, (51%)

L H

(3R,5R,6S, l'R).154

Scheme 478

inanimate objects treated with Queen extracts into their nests as if they were real Queens. Rocca et al. synthesized 155 as shown in Scheme 479.6" The same lactone 155 was identified as a component of the male mandibular gland secretion of carpenter ants (Camponotus pennsylvanicus, C. herculeanus, and C. noveboracensis).626 Jones and Fales synthesized 155 in a straightforward manner (Scheme 480).626

15. Pheromone Lactones

H2f PbEaSO,

0nCOCl 0

1) Ph,P=CH(CH,),Me/THF

xylem, llO°C’

0

O O C H O

-

( 10%)

0

-

233

2)I?’CnHn

(22%)

155

Scheme 419

Pd-C lcymene

l)NFS/CCl,,hv

(@w

2) LiCl , U2C0,. DMF , heal (70%)

155

Scheme 480

F. (E)-7,10-Undecadien-4-olide[5-(3E,B-Heptadienyl)-dihydro-2(3H)furanone] 156 (C, ,HI6O2) This lactone 156 is a component of the smoke-emitted pheromone of male melon flies (Dacus cucurbitae), and it was synthesized by Voaden as shown in Scheme 48 1.627 Mamdapur’s synthesis of 156 was based on three-carbon elongation of

(78%)

EbN / dioxane

1) KOH

2) NaBH,

3) dl. H2S0,

4) heat

> (*). 156

Scheme 481

aldehyde A by two different methods (Scheme 482).628Wilson and Zucker devised a new method for the synthesis of skipped dienes via organosilicon intermediates (Scheme 483).629

The Synthesis of Insect Pheromones, 1979-1989

234

u/\/co2Li

(55%)

v

PCC

\

A

:c,l

d 0

(+)- I58

(35%)

Scheme 482

+ N,CHCO,EI

Me$+

cu, c u m , heat

>

A O * E I

I ) UAIH, p,pcc

'

G. 4-Dodecanolide 157 (C12H2202) This lactone 157 is a defensive secretion of rove beetles (Bredius mandibularis). An efficient synthesis of (f)-157was achieved via five-carbon homologation by the Wittig reaction (Scheme 484).630 0

1 I

n-C,H,,CHO

0

+ CIC(CH,)2COzMe

2 Ph,P*CH,

II 9 Ph,P=CHC(CH,),CO,Me

DMF

t

0 n.C8H,7bC02Me

(71%)

< 0

nC,H

.

n.C,H,, (+)- 157 (68% overall yield)

Scheme 484

2) N a p ,

,,A COzM

I ) NaBH, 2) H' C,H,

1) Ph,P

0

II

BrCH2C(CH,),C0,Me

ti* / PbC

>

0

15. Pheromone Lactones

235

Both the enantiomers of 157 were prepared by Pirkle and Adams by separating the diastereomeric carbamates A and B (Scheme 485) by HPLC.63' Their assignment of R-configuration to (-)-157 was in error.

Scheme 485

Four different chemical asymmetric syntheses of 157 have been recorded. First, Vigneron and Bloy employed a chiral hydride reagent to reduce A to B (Scheme 486), which was converted to (R)-157.590 Noyori et al. employed bi-

c rn p. 76OC Scheme 486

naphthol-modified lithium aluminum hydride for the synthesis of (S)-157 (Scheme 487).632*633 Starting from a chiral sulfoxide, SolladiC prepared (R)-157 (Scheme 488).634Bartlett et al. employed a chiral acetal as the starting material to synthesize (R)-157(Scheme 489).635

236

The Synthesis of Insect Pheromones, 1979-1989

co*Me Me(CHz)/

11 KO,CN=NCO,K AcOH / MeOH

1 OH

n

(S)-157

(aloP-28.7' (MeOH) (76%e.e.)

Scheme 487

?

OH

1) NaOH

Me(CH,),

(95%)

(R)-157

[alOn+32.7O ( M ~ O H ) (86% e.e.)

Scheme 488

KOH

aqTHF-MeOH/ (96%)

1 ) PDC / DMF 2) (n-Bu),NF

3) TsOH / C,H, (60%)

>

Me(CH,),

%"*Go

(W.157

[alDX+a0 (M~OH) (70% e e )

Scheme 489

15. Pheromone Lactones

237

Three chiral syntheses of 157 were executed by reduction with baker’s yeast. Naoshima et al. reduced the sodium salt of 4-oxododecanoic acid to give (R)-157 of 94-100% e.e. (Scheme 490).636They also employed baker’s yeast immo-

(62%) 1) NaOH I W

0

H

(4 1 X)

Me(CH,), \ 8 ‘ o 0

immoklued

w i h xcarrageenan. glucose, 2% HCI aq (26%)

(R)-157

[aIDm+41.1°(MeOH) (94-100% e.e.)

Scheme 490

bilized with ~ a r r a g e e n a n . ~Utaka ’ ~ et al. carefully examined the reduction condition with baker’s yeast and obtained (R)-157[> 98% e.e.; [a]I, 42.4” (MeOH)] in 71 % yield by reducing the potassium salt of the keto A new synthesis of the intermediate keto acid A was achieved by Rao et al., using thiophene as a chain extender (Scheme 491).638By reducing A with baker’s

+

A

(R)-157 lalDn+32.7’(MeOH)

Scheme 491

yeast, they obtained (R)-157,although they erroneously depicted their product as (S)-157. Sugai and Mori synthesized the enantiomers of 157, starting from the en-

The Synthesis of Insect Pheromones, 1979-1989

238

antiomers of 2-aminodecanoic acid B, which was prepared by resolving (*)-A with an amino acylase of fungal (Aspergillus) origin (Scheme 492).639 YCO$

NHCOCH,CI

Amim acyhse

Y CozH

-

___)

NHCOCH,CI

(S)-B

(*)-A

W.6

yCOzH

+

NH,

1) NaN0, dil H2S04

2) CHzN, (47%)

>

1) LUIIH, / THF 2) HBr-AoOH

Me(CHz)7YC02Me OH

(W-A

WCH,),

3) NaOMe / MeOH

(68%)

6

1) CH,(CO,E~), NaOEt / EOH

Me(CH2)760

3) dil H 2 W 4

(7l-W

(S)-157 [a1,'~-37.eO (MH)

lR1-167 .

I

la),20 49.0' (&OH)

Scheme 492

H. (R,Z)-5-Tetradecen-4-olide 158 (C ,4H2402) This is the female-produced sex pheromone of the Japanese beetle (Popifliu juponica). A full paper of the synthesis of the enantiomers of 158 from glutamic acid was published by Doolittle et al. (cf. Scheme 259, Ref. 1).@'" Two other syntheses of 158 were reported starting from optically active natural products. Kang et al. employed D-glyceraldehyde acetonide as the starting material to prepare (S)-A first, which was epimerized to ( R ) - Aand converted to (R,Z)-158 (Scheme 493).641D-Arabinose was the starting material in Nishida's synthesis of (R,Z)-158 (Scheme 494).@* 0

I1

o ~ h + C H o(MeO)2PCH,C0,Me NaHlDME

4-O

Dgiyoeraldehyde amlonide

(8%)

TsCI / C,H,N

(944b)

HO,,W(&O

>

> T~o,o-.Qo

(S1-A

H

o

a

0

(W-A

H, / Pd-C

2)AcOH

+O

p;S/LCO,CH,Ph

'

CF&C'zH

0

-1ooc

(ew

Me(CH,),CH-PPh,

THF-HMPA (41% horn (R)-A)

Scheme 493

>

(74%)

PhCH,OLi

THF (9%)

1) LiOH

Oy'\C02Me

EIOH (9%)

>oHCoo >

(CmI), DMSO E5N

-to

oy\%co2Me

z

( R , )-is8

0

0

[alD" m . 4 O (CHCIJ

E : 2 I 4 :96

'

239

15. Pheromone Lactones

OH

'

-OH HCI

HO 0-Arabinose

1) Me,CO. H'

1) I-BuOKIDMSO

2) NaH , PhCH,Br

2) dil HCI-Me,CO)

HO

>-Ph,P=CHCO,EI

PCC

Ph,P=CH(CH,),Me

CH,CI,

(96%)

AoOH , MeOH

TsoH

Ac20

&on%H,r

MeC(OMe), /CH,CI,

mp. 96-97.5'~

(90%)

(89%)

(90%)

140%

>

MeOXMe

(R,Z)-158 [aloe -70.4' (CHCI,)

Scheme 494

Pirkle and Adams reported a synthesis of 158 by HPLC separation of the diastereomeric carbamates (A and B) (Scheme 495) .63' H 1)

OHC(CH,),CN

1) Me(CH,),CaCLi 2) H,/ Lindar Pd

(96%)

OCN

HO

>

Me(cHz)$'A

(cH2)2CN

2) HPLC sew.

>

( S , 2 )-158 [a]?' t70.3' (CHCId

B (36.5%)

Scheme 495

Four different groups of workers employed chemical asymmetric reduction for the synthesis of (R,Z)-158. By using the asymmetric reducing agent B-3pinanyl-9-borabicyclo[3.3.Ilnonane (A, Alpine borane@), Midland et al. syn-

240

The Synthesis of Insect Pheromones, 1979-1989

thesized 158 in two different ways (Schemes 496 and 497).59'3643 The latter

H H

Me(CH2),C=CCH0

UClCC02Et

H H

THF

Me(CH2)7

0

r.1. 6h

OH

aged Pd

(87% e.e.)

(R,Z)-158

(38%9.e.)

Scheme 496

H'

Me(CH2),CZC

Do

H2/ Pd-CaCO,

Pb", quindine (R,Z)-158 69.9'

(CHCI, )

Scheme 497

process yielded pure (R,Z)-158 because it was possible to purify the intermediate B by recrystallization. Baker and Rao also used Alpine borane@ for their synthesis of (R,Z)-158 (Scheme 498).644They purified an amine salt of the phthalic half ester A by recrystallization and obtained pure (R,Z)-158. Noyori's

15. Pheromone Lactones

-

Me(CH,),CIC L

THF

d c

0

,

k

&.o

THF r.I.3days (70%)

n

, CSHSN

2)dl HCI 0

%cozk

Me(CH2)7CE+C02k

(74% e.e.)

C

(68%)

1)

H. OH

3~0,~

0

1) EtMgBr / THF

241

Me(CH,),Cn

4) Aectysrn

5) dil HCI (24%)

1) NaOH aq 2)AcOH

(*1009/. e e )

A

H, / Pd-CaCO, Me(CH,),CIC penlane

(WX)

Scheme 498

binaphthol-modified lithium aluminum hydride was also used to prepare 158 (Scheme 499).632*633 Senda and Mori reduced keto ester A with lithium alu-

lalorn -51.2' (CHCI,) (73% e.e.)

Scheme 499

minum hydride-Darvon alcohol (Chirald@)B to give C of 79-85% e.e. (Scheme 500).645This ester C was hydrolyzed, and the resulting acid was found to give crystalline salt D. Its recrystallization yielded pure material, which finally furnished enantiornerically pure (R,Z)-158. This process was employed, with a small modification, for the multi-kg synthesis of (R,Z)-158. Chandrasekaran and his co-workers published a synthesis of (+)-158 (Scheme 501).646However, (&)-lSS is biologically inactive.w0

242

The Synthesis of Insect Pheromones, 1979-1989

-100C-65°C

OH Me(CH,),C=C -COzMe

1) NaOH

(97%)

OH

2) dl HCI

3)

C (78.6%e e.) 4) Rectyst'n

(65%)

D m.p. 9 0 . 9 1 ~ ~

H, I Pd.CsC03 Me(CH,),CSC

C,H,,.

-

quinoline

(72%)

0

0

(R,Z)-158

[aJoz'.70.4' (CHCi,) (-100% e.e.)

Scheme 500

(52%)

Unstabk,

H, I Pe-BaSO, quindine (95%)

(fbl58

Scheme 501

I, (R)-5-Hexadecanolide 159 (CI6H3,,O2) This 6-lactone 159 was isolated from heads of the Queens of the oriental hornet (Vespa orientalis) as a pheromone for the workers to stimulate the construction of Queen cells. Bioassay of Mori's synthetic enantiomers of 159 by Ishay proved only (R)-159 to be b i o a c t i ~ e . ~ '

15. Pheromone Lactones

243

Two new syntheses of (f)-159have been reported. Bacardit and MorenoMafias prepared (*)-159 starting from dehydroacetic acid A (Scheme 502).59y*m8 Samarium(I1) iodide-induced Barbier-type reaction was employed by Otsubo et al. for the preparation of (*)-159(Scheme 503).619

1) NaNHz/ NH,

2, Ks(CHz)aBr

A

90% HzSO,

Me(CH,),,

130%

(74%)

H, / Raney-Ni Me(CH,),, (84%)

(4% overdl yield)

(86%)

A0

0

C ~ H heal ~ (85%)

(f)-159

Scheme 502

Br(CH,),CO,EI Me(CH,),,CHO

Sm121HMPA (44%)

WCH,),, 0

0

(f).159

Scheme 503

Nineteen different syntheses of optically active 159 have been reported as detailed below.

(1) Syntheses Starting from Chiral Building Blocks Larchevgque and Laland prepared (R)-159 starting from (S)-glutamic acid (Scheme 504).650Gerth and Giese synthesized (R)-159by radical carbon-carbon

The Synthesis of Insect Pheromones, 1979-1989

244

(S)-Glulmic Acid

(66%)

(61%)

heal

(R)-159

(91%)

m.p. 4OoC

[aIDu 4 8 . 5 ’

(THF)

Scheme 504

bond formation using a chiral radical precursor prepared from (R)-glyceraldehyde acetonide (Scheme 505).605

(55%) OTHP TsO&CO,hk

(2) Syntheses by Means of Optical Resolutions Pirkle and Adams prepared the enantiomers of 159 by HPLC separation of the diastereomeric carbamate (Scheme 506).63’ The specific rotations of their products, however, were smaller than those reported by others. Mori and Otsuka also employed resolution of the intermediate for the preparation of the enantiomers of 159.65’In this case, the starting (f)-2-chloroacetaminotridecanoic acid (A) was resolved with amino acylase to give (S)-2-aminotridecanoic acid (B) and @)-A (Scheme 507). The synthetic enantiomers of 159 were tested by Ishay against the oriental hornet and (R)-159was found to be b i o a c t i ~ e . ~ ~

15. Pheromone Lactones

i

(70%)

[alon

(59%)

(96%)

Ho Me(CH,),,~oH

m.p. 31.32OC

(94.5%)

0

1)HBrlAcOH 2) N a O k I MeOH

- 2 4 . 1 ~(THF)

CUBllHF

Me(CH,),,A

(94%)

(94%) 1) o3/ Me,co

HO

A c p / CH ,N ,

2) Jones CrO,

OAc "

(

c

H

2

)

l

o

~

3) KOH / a q THF

4) Reaysrn

(66%) HO

TsOH / CH ,,

Me(CH2)10LC02H

m.p. 87-68' (-100% e.e.)

Me(CH,),,'"

(54%)

(R)-159, m.p. 37OC [a]:'.' 40.2' (THF)

'

245

246

The Synthesis of Insect Pheromones, 1979-1989

(3) Syntheses Based on Chemical Asymmetric Reactions Three enantioselective syntheses of 159 have been reported based on the chemical asymmetric reduction of a carbonyl function. Kikukawa and Tai employed catalytic hydrogenation over tartaric acid-modified for the reduction of the carbonyl group, and secured pure enantiomers of 159 in high overall yield (Scheme 508).653Kosugi et al. synthesized (R)-159 by means of highly 1) H2

Tartaric acMm o d R d Ni

0

(R).A

31puriRcaCon

1) CH2N2

OH

Me(CH2),o~CozMe

m,p, 7&71,5°C

[aIDQ-16.2'

OTHP M~(CH,),,&~~Z~~

(CHCI,)

(-100% e.e.) 1) UAIH,

OTHP

LiCH,CO,U

TsOH

OTHP

?

2) TSCI/C~H~N> M e ( C H 2 ) , o ~ B ~ ~ ~ M e ( C H 2 ) l o ~ C o z L i

(389/lrm A)

3) UBr / Me2C0

(R)-159 m.p. 36.5-37°C

(S)-159 m.p. 3B°C

[alDm+39.a0 (THF)

[ Q ] ~ " -41.0'

(THF)

Scheme SO8

-

diastereoselective reduction of chiral 0-ketosulfoxides under chelation control (Scheme 509).654Taber et al. employed a chiral alcohol A, which was designed

T

0 I-BuO,C(CH,),CO,Me

t

UCH,

""'OMe+

I.BuO,C(CH,),

T L;: ""0 , 0

(60% from A )

(64%)

_ _

(R)-159 m p . 40.4loC [atD +39.5O (THF)

Scheme SO9

(i-Bu)filH

Me

A 1) Zn.Me,SiCI C,H,N.THF

0

ZnC121THF

-loooc

15. Pheromone Lactones

247

to block one face of the carbonyl group of the keto ester B, as the chiral auxiliary to achieve highly enantioselective synthesis of (8)-159 (Scheme 5 lo)?

(87%)

B

1) 0,/ MeOH

2)Me

s

2 3) PCC.NaOAc. MS 4A / CH,CI,

(S)-159 m.p. 38.539.5"~ -37.l0(THF)

(67%)

Scheme 510

Four chiral syntheses of 159, as detailed below, were based on chemical asymmetric reactions other than carbonyl reduction. SolladiC and MatloubiMoghadam employed aldol-type reaction between a chiral sulfoxide and an aldehyde for the synthesis of (S)-159 (Scheme 5 l l p 4 By resolving 2-undecyln -

T

SvC02BU1

+

Me(CH,)&HO

(40% from A)

(S)-159 m.p. 30-31 OC

lalDn +27.e0 (THF)

Scheme 511

248

The Synthesis of Insect Pheromones, 1979-1989

cyclopentanone via its acetal with (2R,4R)-2,4-pentanediol,Yamamoto et al. synthesized (S)-159 (Scheme 5 12)? Another unique synthesis of (R)-159 by

MCPBA

WCH,),,

CHCI,

(75%)

0

0

(SF159

[a],,loar -38.3' (THF)

Scheme 512

Oda et al. employed a new asymmetric lactonization reaction using a C,-chiral auxiliary (Scheme 5 13).6J7Kapadi prepared (R)-159 of low enantiomeric purity

1% CF,CO,H

m

N

H

,

1) Ac,O / CH ,N ,

1) (COCI),,Dh!SO,E$N

/CH,CI,

Scheme 513

NHAc

15. Pheromone Lactones

249

by alkylation of an asymmetric enamine followed by the Baeyer-Villiger oxidation of the resulting optically active ketone (Scheme 5 14).658

AIEl

n-BuO n-Bu&

i+rMgBr, THF

(80%)

(-HzO)

(WW MCPBA

1) Me(CH,),oI.-78'C

>-

CHpCIZ

Me(CH,),i''

(9W

(6ff4

(R)-159 m.p. 2S3O0C

lalon +zo.~' (THF)

Scheme 514

(4) Syntheses Based on Biochemical Asymmetric Reactions Eight chiral syntheses of 159 were based on biochemical asymmetric reactions. Semi synthesized the pure enantiomers of 159 starting from the diol A (Scheme 515), which was prepared by the reduction of cinnamaldehyde with baker's p

C

H

0

l)wMea

glucase (16.25%)

+

+ &

2) Separation (chromalog.)

B HO

OH

&

$+

H S : o

H

OH

OH

C

( 4 : 6 ) 1) HIO, / THF

NaH / DMF

2) NaBH, I MeOH

heal

3) TSCI / CH ,N , (67%)

OCH,Ph

(so%)

x

A

x

H --E r---

1)PhCH,Br

HO

\

lTHF

T

Tso-

(63%)

(S)-159

B

Scheme 515

m.p. 40-41OC [aloQ-39.2' (THF)

i

/

OCH,Ph

(R)-159 rn p 40-41OC [a]o" 4 9 97' (THF)

250

The Synthesis of Insect Pheromones, 1979-1989

(R)-159 m.p. 39%

(49%)

[,IDm

+40.B0(THF)

yeast.G59Fujisawa et al. prepared a chiral epoxide C (Scheme 516) starting from A, the reduction of which with baker's yeast furnished optically active alcohol B.G60The epoxide C was converted to the enantiomers of 159 (Scheme 516).6G0 Furstoss and his co-workers achieved an enantioselective microbial Baeyer-Villiger oxidation (Scheme 517).G6'By this method, (S)-159 and (R)-B were obtained. Chemical Baeyer-Villiger oxidation of (R)-B would give (R)-159.'f.G5G 0

& (*)-A

Acineiobacler CBlmacBlicOs -

NClB 9871 (CHz)ioMe - M e ( C H & o O (precu~urem

+

OH)

(S)-ISO (25?4)

.29,8'(THF)

.

(74%e.e.)

Me(CH&"

0

(R).B (36%) [alD26-n.00[E$o)

(959he.e.)

Scheme 517

Five papers reported the enantioselective reduction of 5-oxohexadecanoic acid with baker's yeast. Naoshima et al. prepared (R)-159 (ca. 40% e.e.) by yeast reduction of the keto acid (Scheme 5 18).594They could later improve their

15. Pheromone Lactones

251

(60%) 1) N a O W W H

mw

n

m.p. 2430OC [alDm+15.80(THF)

1) bakeh yeast immobilized

in carageenan glucose, 2% KCI aq

0 L C O , N a

WCH,),

2) dil HCI pH 2-3

'

MsW,),

L

HO C

O

,

H

(32%) CF,CO,WCH,CI, Me(CH,),,Y'

(75%)

(R)-159

m.p. 37.38'~

[ a ] ~ ' "+42.4'(THF)

Scheme 518

method to obtain pure (R)-159 (ca. 100% e.e.) by employing baker's yeast immobilized in carrageenan and reducing the sodium salt of the keto acid (Scheme 5 18).636 Reduction of potassium 5-oxohexadecanoate with baker's yeast was also highly enantioselective to give (R)-159, m.p. 37.5-38"C, 39.5" (THF), in 40% yield.637s662 Bhalerao et al. reported a new synthesis of 5-oxohexadecanoic acid using thiophene as a chain extender (Scheme 519).638

+

1) K O W W 2) bakeh yeast

3)H'

> MeGH,),;" (R)-150 m.p. 31'C

[.o ln

+27.B0(THF)

Scheme 519

252

The Synthesis of Insect Pheromones, 1979-1989

J. (SR,6S)-6-Acetoxy-5-hexadecanolide160 (C,6H3204) The major component of the oviposition attractant pheromone from the apical droplet of eggs of the Southern house mosquito (Culex pipiens fatiguns) was shown by Laurence and Pickett to be erythro-6-acetoxy-5-hexadecanolide 160.663The natural pheromone was later shown to be (5R,6S)-160, by comparing Mori’s synthetic enantiomers with the natural pheromone.664

( I ) Syntheses of (&)-I60 Seven syntheses of (&)-160have been reported. Laurence and Pickett were the first to synthesize ( f )-160 by cis-hydroxylation of (Z)-5-hexadecenoic acid as the key-step (Scheme 520).663 Yamaguchi and Hirao used their new alkynyla-

tion reaction of epoxy alcohols derived from (E)-allylic alcohols for the synthesis of (f)-160(Scheme 521).665Thus, lithium acetylide in the presence of

(*)c m.p. 127%

(*)-I60

Scheme 521

15. Pheromone Lactones

253

boron trifluoride etherate reacted with epoxy alcohol (+)-A to give eryrhroglycol (+)-B, which was converted to (+)-160 via (*)-C. Ochiai et al. prepared (f)-160by using oxidative 1,4-fragmentation of y-stannyl alcohol with iodosylbenzene as the key-step (Scheme 522).666*667 The stereocontrolled ad-

(82%)

1) MCPBA

2) heat

3) AcpC5H5N (40%)

OAc (f).tW

Scheme 522

dition of decylmagnesium bromide to acrolein dimer was the key-step of Jefford's short and efficient synthesis of (+)-160 (Scheme 523).668Suzuki and his

(84%) 2) chromalog.

5.67

1) Ac,WC,H,N 2) PCC

OAo

Scheme 523

:

1

254

The Synthesis of Insect Pheromones, 1979-1989

co-workers employed the Michael-type reaction of B-iodo-9-BBNlethoxyacetylene adduct to a,@-unsaturated ketone to prepare a 1 : 1 mixture of (&)-160 and its threo-isomer (Scheme 524).669Dawson et al. published a simple syn-

H2C=C-C’O M ‘U

t

OHC(CH,),Me

1) Ac20 2) HCI

>

~ ( C H Z ) O M OAc

Scheme 524

thesis of an isomeric mixture of (f)-160and its threo-isomer by means of aldol reaction, followed by Baeyer-Villiger oxidation and acetylation (Scheme

525).670

6 Osik3

OHC(CH,),Me T,CI,/CH,CI, -78OC

’

MCPBA ~ ( c H 2 ) S M .

CH2C4 (86%)

’

(*).I60

Scheme 525

(2) Syntheses Based on Biochemical Asymmetric Reactions Biochemical asymmetric reactions were used in three syntheses of optically active 160. The first synthesis by Fuganti et al. employed chiral aldehyde A (Scheme 526) as the starting material, which was prepared from cinnamaldehyde by yeast reduction.67’ Their synthesis provided all of the four possible

15. Pheromone Lactones

1) NaH,PhCH,B/DMF C

2)

AcOH-MeCN

-

'n H?

OH

HIO,

(CH,),Me

THF

(60%)

OCH,Ph

(76%)

D

OCH,Ph OHCX

(CH,)&el

(>950/oe.6.)

E

(23) 1)

D

255

,

o3oxid'n

Me(CH,),

DMF

2) HdPd-C

OAc

(want)

3) Ac,01C,H5N

(5R,6S)-160

(65%)

[aIDxI-37.6'

(5R,6R)-160

[alDmt14.40 OAc

(5S,6R)-160

(5S,6S)-160

[alDxI +so

-14.2'

Scheme 526

stereoisomers of 160. Tsuboi et al. reduced (f)-chloroketo ester A (Scheme 527) with baker's yeast and obtained B and C after HPLC separation of the CI

1) bakers yeast glumse (75%)

CI

M ~ ( c H ~ ) , ~ ~ ~ * ~ ~ 0

? &/cop ikCoZEt

~(CHZ),

OH

OH

B

A

(48:52)

(>95%e.e.)

D

Scheme 527

i

+

C (>95%e.e.)

256

The Synthesis of Insect Pheromones, 1979-1989

mixture.672The hydroxy ester C could be converted to the epoxide D. Because D was converted by others to (5R,6S)-160 (vide infra), the present preparation of D implied a formal synthesis of it. Rahman et al. prepared the antipode of the natural pheromone by the photochemical method (Scheme 528).673The chiral starting material A was prepared biochemically.

.

.

nelural pheromone)

Scheme 528

(3) Syntheses Starting from Chiral Building Blocks Eight different syntheses of optically active 160 were achieved starting from chiral natural products. Masaki et al. employed (+)-diethy1 tartrate as the starting material (Scheme 5291, providing the antipode [(5S,6R)-160]of the natural

Na/EDH THF (75%)

HO

1) Ac,O/C,H,N 0

2) MCPBA. BFiEbO

OH

(CHz)em

CH,CI,

EgN (59%)

OAc (5S.6R).160

[a],t42.0°(CHCI,)

Scheme 529

15. Pheromone Lactones

257

pheromone.674 Kotsuki et al. prepared (5R,6S)-160 from (-)-tartaric acid (Scheme 530).675Machiya et al. started from the enantiomers of glyceraldehyde

Scheme 530

acetonide to synthesize all of the four isomers of 160 (Scheme 53

(5R,6A)-160

lalo" +14.io(CHCl.J

(5R.65)-180

39.O0(CHCIJ

Scheme 531

(6S,65)-160

[a]," -13.0°(CHClJ

Bioassay

The Synthesis of Insect Pheromones, 1979-1989

258

of their four isomers on C. pipiens molestus showed (5R,6S)-160 to be the most active attractant. 676 Kang and Shin synthesized the antipode [(5S,6R)-160] of the natural pheromone starting from 2-deoxy-~-ribose(Scheme 532) .677 Rokach et al. prepared the enantiomers of 160 also from 2-deoxy-~-ribose(Scheme 533).678s679 The

HO P

O

5

H

(6W)

OH

>

Ph,P-CHC02Et P

O

H

+O

DME, PhCO,H

>> z : : c C O z E t

(91%)

PDC

(78%)

2-Deoxy-D-ribose CHO

Me(CH,),P'Ph,W

> ~ ~ ~ L c o , E n-BuLilTHF t ( S W

(41%) 1) LOWaq THF 2) aq AcOH

3) TsOWC,H, (84%)

'

M . ( c HHO z ' o y * ~ o

OAo

(87%)

(55,6R)-160

Scheme 532

OH HO OH

Ph,P=CHCO,CH$h THF

>

OH OH -CO,CH,Ph i

[ujo2O+34.5°(CHC1J

C6HsN 2) HdP&C

on

', 6H

[a], -38.5'(CHCI,)

(5S.6R)-180 [alD O C )+ ~ .S H (Z ,C II

Scheme 533

15. Pheromone Lactones

259

notable feature of their synthesis is the inversion of configuration of the contiguous carbinol centers by means of the Payne rearrangement (A B).678Kang and Cho employed a radical carbon-carbon bond formation for the synthesis of (5R,6S)-160 from 2-deoxy-~-ribose(Scheme 534).680Ichimoto et al. synthe+

Scheme 534

sized (5R,6;)-160 in 12.7 % overall yield from 2-deoxy-~-ribose (Scheme 535).@"Kamikawa et al. used D-ribose as their starting material, and prepared (5R,6S)-160 in 9.1 % overall yield in 10 steps (Scheme 536).682 OMe

1) TsCVC,H,N

OH

1) PDCIDMF

2) AcOH 3) Ac,O/C,H,N

(78%)

(65%)

n OAc

Scheme 535

(4) Syntheses Based on Chemical Asymmetric Reactions

The Sharpless asymmetric epoxidation was applied in four syntheses of (5R,6S)-160. Mori and Otsuka synthesized both (5R,6S)-160 and (5S,6R)-160 by asymmetric epoxidation of (*)-A to give either (+)-B or (-)-B (Scheme

The Synthesis of Insect Pheromones, 1979-1989

260

OHOH

D-Ribose

(83%)

(69%)

o2

(99.5%)

no [aloteponed

Scheme 536

537).683Lin et al. prepared all of the four stereoisomers of 160 by asymmetric epoxidation (Scheme 538).684A very short synthesis of the enantiomers of 160 was reported by Barua and Schmidt (Scheme 539).685Optically active epoxide B as prepared from (&)-A by the Sharpless procedure was acetylated to give C, which was treated with 0-lithiated P-ethylthioacrylate to give lactone D. This was reduced with Raney nickel to furnish 160.685In Kametani's synthesis of (5R,6S)-160, the beginning step was the kinetic resolution of 1-(2-furyl)- 1-

1)A$O/C,H,N

(5R. 6s)-160 [a],2'~5-38.50(CHCI,)

(SS, 6R)-160 [a],2"5+38.80(CHCI,)

Scheme 537

15. Pheromone Lactones

(97% 9.9.)

261

(5R,6S)-160

[a], -37.4'(CHC13)

(S,6R)-160 lalo+37.2'(CHCI3)

(5R.6A)-160

[a], +14.6°(CHC13)

(5% 6S)-160 (a],-14.l0(CHCl3)

Scheme 538

undecanol by the Sharpless protocol (Scheme 540).686,1228 They, however, did not prepare the pheromone itself, but interrupted their synthesis at the stage of the hydroxy lactone. Wang et al. prepared (5R,6S)-160and (5S,6S)-160starting from cyclohexane-l,2-diol (Scheme 541).687The key-step was the kinetic resolution of ( f ) - B to give (S)-B. Other asymmetric chemical reactions were employed in the following three works. Asymmetric reduction of 2-cyclohexen- I -one with the chiral reducing agent (Scheme 542) to give (S)-2-cyclohexen-l-ol was the starting step in Fujisawa's synthesis of both (5R,6S)-160and (5S,6R)-160.688 In the synthesis by KO and Eliel, reduction of oxathiane A yielded B, which was converted to

262

The Synthesis of Insect Pheromones, 1979-1989

Scheme 539

(87%) 4.6

L

1

15. Pheromone Lactones

96% 8.8.

n

0

1IKOH-MeOH

(87%)

0

__j __j

OAc

(5s.6R).160 [ a 1 ~ ~ +1°(CHCI,) 39.

Scheme 542

263

264

The Synthesis of Insect Pheromones, 1979-1989

(5R,6S)-160 through a lengthy route that included inversion of configuration at C-5 (Scheme 543).689Zhou et al. prepared (5R,6S)-160 and (5S,6R)-160 by

1)NaHnHF PhCH,B

LiBH(6-Bu) OH

2)chrornalog.

B (82% d.e.)

(95%)

(92%)

95

O

:

5

(80%)

1)KOWaq EtOH H

(8%)

(98% d.9.)

(84%)

(78%)

NCS*AgN03 ____j NaHCOJaq Me,CO

(CH,),Me

&O%CHzph

2

OCOPh C 4 (CH,),Me

6CHzPh

A

2)TsOH/CeH, 3)HJPbC 4)Ac,O/DMAP (7004

Me(cHz)Q~o OAc (5R, 65)-160 [~tJ~~-37.2~(CHCl,)

Similaiiy (5R. 6R)-160. [ c 1 ] ~ ~ + 1 4 . 4 ~ ( C H and C l ~ )(5s. . 6Rp160, [ ~ ] ~ ~ + 3 7 . 2 ~ ( C H Cwere l , ) , prepared.

Scheme 543

employing asymmetric addition of a chiral sulfoxide @-TolSOCH,CO,Bu') to (R)-(+)-2-benzylo~ydodecanal.~~~ The efficacy of (5R,6S)-160as the mosquito attractant was demonstrated in western Kenya, and the possibility of using this material in combination with a safe insecticide was ~ o n f i r m e d . The ~ ~ ' pheromone (5R,6S)-160was active against not only the southern house mosquito [C. pipiens fatigans (= C. quinquefasciatus)] but also C. tarsalis, while it was inactive against the yellowfever mosquito (Aedes aegypti) and the common malaria mosquito (Anopheles q u a d r i r n a ~ u l a t u s )Substitution .~~~ of the acetyl group of (5R,6S)-160 by fluoroacetyl resulted in the preparation of a strong oviposition attractant against the southern house mosquito (C. pipiens f ~ t i g a n s ) . ~ ~ ~

15. Pheromone Lactones

265

K. Ferrulactone I1 [(3Z,11S)-3-Dodecen-ll-olide] 161 (C,2H2002) This is a component of the aggregation pheromone of the rusty grain beetles (Crypfolestesferrugine~s).~~~ Oehlschlager et al. prepared (+)-161, (R)-161, and (S)-161 employing propylene oxide as the chiral source (Scheme 544).695

c I-l

I '

n-OulillHF-HMPA (62%)

(46%)

1)MEMCI. EINPr; CH,CI,

gH

P

o

.

&

+

2)AcOWaq THF

I

OH V

(72%)

HdP-2 NI C

0

z

3)

H

OMEM

'

O H -

w C 0 2 H

(83%)

OH

-

s-s

-

EOH

Sirnilam:

00 (5%)

OH

___3 H,N(CH,),NH2

1) Jones CrO, ____3 2) Zn&~CH,CI,

CO,H

H (S)-161

-

Ph,P.AgCO,/

MeCN-xylsne

(28%)

(R).161

(a]Op~'-780(CHC1~

[a)oP~'+70.50(CHCI,)

Scheme 544

Mori et al. employed ethyl (S)-3-hydroxybutanoate as the chiral source and prepared (S)-161 (Scheme 545).696Oehlschlager et al. subsequently reported an improved synthesis of the seco-acid (Scheme 546).697It was later found that enantiomerically pure (S)-161 is produced by C. ferrugineus, while @)-I61 is produced by the merchant grain beetle (Oryzaephilusrner~ator).~~~ L. (2)-3-Dodecen-12-olide 162 (CI2HZ0O2) The flat grain beetle (Cryptolestespusillus)is a worldwide pest of stored products. Millar et al. isolated and identified three macrolides as its aggregation pheromone.699 (Z)-3-Dodecen-12-olide (162) was the major volatile and was

266

The Synthesis of Insect Pheromones, 1979-1989

Y

-

-CO,H

s-s

Ph3P,AgCIO,/MeCN toluene, heal (CN&

24%;

H

(S)-161

13.3% after dlslilh)

[a]Dn+92.20(CHC13)

Scheme 545 NaNH,

.

(94%)

.

(95%)

OH

OH

+

lq NH,-THF

-co2n

(S)-161

Scheme 546

active alone. (5Z, 13S)-5-Tetradecen-l3-olide(165) was not active alone, but synergized the response to 162. (32,62)-3,6-Dodecadien- 12-olide (163) was active alone at higher concentrations, but did not significantly increase the response when added to the most active mixture of 162 and 165. Millar et al. synthesized 162 by means of acetylenic chemistry followed by the Corey ma-

15. Pheromone Lactones

267

crolactonization (Scheme 547).700The seco-acid A was later prepared in a more

l)ElMg&

a

2)

-Q

, MEMO

JonesCrO,

F

C

-

CO,H

Ph,P/xylene heal (33%)

A

2

c_3

H Z)HZ/P-~ Ni (81%)

162

l)&dCH,CI,

1)n-BuLirTHF

2)KOH, 18amvn-S

B

(Wmt)

(74%)

D

C

H,- OH P-2 NI

0

(67%)

-OH

- OH

1)HCllaq THF

MEMO

-

(3:2-4:l)

E

C02H

A

Scheme 547

efficient manner starting from 10-undecen- 1-01 (B).697 The key-step was the deconjugation of a,P-alkynoic acid C to a mixture of P,y-alkynoic acid D and allenic acid E, which was semi-hydrogenated to A (Scheme 547). Mori et al. employed the acetylene zipper reaction for the preparation of the 1-alkyne B from A (Scheme 548).70'

M. (32,62)-3,6-Dodecadien-12-0lide163 (C12H1B02) The sawtoothed grain beetle (Oryzaephillus surinamensis) produces as its aggregation pheromone (3Z,6Z)-3,6-dodecadien-12-olide (1631,(32,6Z, 1 1R)-3,6dodecadien-1 1-olide (164), and (52,8Z, 13R)-5,8-tetradecadien-l3-olide (166).6989702 Millar and Oehlschlager prepared 163 by the standard acetylene chemistry followed by the Mukaiyama cyclization (Scheme 549).703 They later reported an alternative and more efficient synthesis (Scheme 550).697

268

The Synthesis of Insect Pheromones, 1979-1989

Ph,P/kylene heat (32%)

Me(CH,),CaCH

-

162

n-@ulillHF

Scheme 548 KH

>-

Me(CH2),CICCH,0H

(CH$Xn (95%)

MEMCI

> -EINP~,

+

MEMO-

(95%)

-O H

H,N(CH,),NH,

+

(46%)

l)EIMgBrnHF, CuBr

TsO

-

2)TsOH. MeOH

OH

, , &+

3 MEMO

I

(56%)

1)Jones cro,

V 2)HCUaq THF (44%)

H,

HO

C02H

P-2 Ni

- OH

- -

C0,H

Scheme 549

N. (32,62,11R)-3,6-Dodecadien-ll-olide164 (Cl,Hl,02) This is the aggregation pheromone of Oryzaephillus surinamensis and 0. mercar0r.702~704 Millar and Oehlschlager synthesized (+)-164as shown in Scheme 55 1.703 By slightly modifying the procedure, they also synthesized (S)-164, which was inactive as the p h e r o m ~ n e .The ~ ~ natural pheromone was pure (R)-164.698.704 Oehlschlager et al. reported an alternative synthesis of 164

15. Pheromone Lactones

269

__j

663

Scheme 550

3)TsOWMeOH (66%)

H p 2 Ni

0

-CO2H unslable

EDH

(35% horn keto add)

(Scheme 552).6'7 Due to the unstable nature of the diyne intermediates, neither of the two routes was efficient enough.

0. (SZ,13S)-5-Tetradecen-13-olide165 (C14H2202) In Millar's synthesis of both (R)-16S and (S)-165, the enantiomers of propylene oxide were employed as the chiral building blocks, and the final lactonization

270

The Synthesis of Insect Pheromones, 1979-1989

OMEM O H-

HCI

aqTHF

OH O H184

was carried out by the Mukaiyama procedure (Scheme 553).700Only (S)-165 was found to be produced by the flat grain beetle (C. p u ~ i l h )while , the grain beetle ( C . turcicus) produces a 33:67 mixture of the R- and S - i ~ o r n e r s In .~~~

y

l)MEMCI, EINPr', 2)HdP-2 Ni

@Bit B)AcOH/aq THF

>

H O-

F

OMEM

(78%)

(5)-165 (a]D~~49.60(CHC13)

(R)-165

[a]o"-46.40(CHCIJ)

Scheme 553

-

1)PDCIDMF 2)HCVaq THF

(72%)

15. Pheromone Lactones

271

C. turcicus, 165 functions as a synergist of (52,8Z, 13R)-5,8-tetradecadien-l3olide (166).705Mori et al. employed ethyl (S)-3-hydroxybutanoate as the starting material for the synthesis of (S)-165.70'In their synthesis, acetylene-zipper reaction (A --t B, Scheme 554) was the key-rea~tion.~"Naoshima et al. syn-

(75%)

OH

1)n-BuLflHF-HMPA

B

-

(91%)

OH

i)A+O/C,H,N

OTHP

2)AoOWaq THF

thesized (S)-165 by reducing keto acid A to hydroxy acid B with immobilized baker's yeast (Scheme 555).706 A full paper of this work has been published.'0s9

P. (SZ,8Z,13R)-5,8-Tetradecadien-13-olide 166 (C14H2002) This is the aggregation pheromone of the grain beetle (Cryptolestes t u r c i c ~ s ) . ~ ~ ~ The natural 166 is a mixture of R- and S-isomers in a ratio of 85: 15.698It was active alone and synergized by 165, which is inactive by itself.707Oryzaephillus ~ ~ ~ .and ~ ~Oehlschsurinamensis also employs (R)-166 as the s y n e r g i ~ t .Millar lager synthesized (*)-166, (R)-166, and (S)-166 (Scheme 556).703 An improved synthesis of (f)-166 was later recorded by Oehlschlager et al. (Scheme 557).697Pure (R)-166 and (S)-166 were inactive against C. turcicus, but mixtures of (R)-166 and (S)-166 were active.707

The Synthesis of Insect Pheromones, 1979-1989

272

(!a%) 0

-

---+A - WCO,H 2)H30' i)NeOH

0

1)KOH aq

2)bakerr yeast enbspped in Calaum Alginare

A

(67%)

-

-co$I

B (95% e.e.)

(40%)

(S).165

[a],n+52.So(CHCia)

Scheme 555

(64%)

m

0.lii-t-

1) HdP-2 Ni

C

0

,

H

2) AcOH/aq THF (53%) (27% overall yield)

OH

> A n r-v --A /

166 (R)-166 [RIDN 4.4'(CHCI3)

(S)-leS [slog + 4 M 0 (CHCI,)

Scheme 556

COzH

16. lsoprenoid Hydrocarbons as Pheromones 1) ErMg

1) TsCVKOH. EtzO

Jones’CrO,

>

2) dil HzSO,/MezCO

A

0

OMgEr

CuCLrlHF-HMPA

2) UBr/MezCO

m

C

O

273

z

H

> -N a W , €OH

(87%)

OH m

C

0

2

OH -CO,H

“2

P-2 Ni

H

-

-

(73%)

(*).158

Scheme 557

Chirality of these macrolide pheromones of Cucujidae grain beetles and its implications for species specificity were discussed by Oehlschlager et al. 698.704.708

16. ISOPRENOID HYDROCARBONS AS PHEROMONES

167 and (Z,E)-a-Farnesene 168 [(3E,6E)and A. (E,E)-a-Farnesene (3Z,6E)-3,7,11-Trimethyl-1,3,6,lO-dodecatetraene] (C15H24) These are the terpenoid trail pheromone components isolated from whole worker extracts of the red imported fire ant (Solenopsis i n v i c t ~ ) . ’Vander ~~ Meer et al. synthesized the farnesenes by dehydrating (E)-nerolidol (Scheme 558).709The

or DMSO, 1W°C (35%)

188

(E)-Nerdidd (

188

187

17

36

Scheme 558

29

I

274

The Synthesis of Insect Pheromones, 1979-1989

isomers were separated by Florisil chromatography. (E,E)-a-Farnesene (167) was highly active at the dose of ca. lo-’’ g/cm against the ants. Significant trail-following activity was shown by (2,E)-a-famesene (168)at g/~m.~”

B. (E)-0-Farnesene[(E)-7,11-Dimethyl-3-rnethylene-1,6,10dodecatriene] 169 (C 15H24) This is the alarm pheromone of the cotton aphid (Aphis g~ssypii).~’~ Nakai and his co-workers prepared 169 from myrcene employing an allylic carbamate as an intermediate (Scheme 559).481Starting from 2-(hydroxymethyl)-4-(phenyl-

169

Scheme 559

thio)-1-butene, Mandai et al. synthesized 169 (Scheme 560).7” Kang’s synthe-

/THF.HMPA

+,,,

3) 61 HCI

, Hocuz

\

OAe

I O

H

C

USPh

EgN

(8%)

Me,C-PPh, THF

SPh

(94%)

2) NaHCO@luene

heat (8W

189

Scheme 560

(77%)

16. Isoprenoid Hydrocarbons as Pheromones

275

sis of 169 started from linalool (Scheme 561).712Szhntay's synthesis of 169

;y>

m(OEt), OH Linabal

1) LHIH, 2) PCC

&CO,Et

(61%)

E:Z=97:3

A

C

H

O

(6'W

Scheme 561

(Scheme 562) was simple and efficient, starting from geranyl

Geranyl bromide

Far-

HMPA

(70%)

16s

Scheme 562

nesol was converted to 169 in two steps by Kang et al (Scheme 563).'14 Mo-

iseenkov and his co-workers achieved a two-step synthesis of 80% pure 169 from myrcene (Scheme 564).715Kawashima and Fujisawa's synthesis of 169 used an unsaturated lactone as the starting material (Scheme 565).7'6 Baeckstrom et al. converted myrcene into 169 in 19.5%overall yield (Scheme 566).717

276

The Synthesis of Insect Pheromones, 1979-1989

/k&& myrcene

169

PhSOCl I ZnCI, '

I.PrNO,. -20°C

(W4

'

CuIfrHF SOPh

(34%)

(E:Z-4:1)

Scheme 564

(54%)

169

Scheme 565

(91%)

(69%)

Scheme 566

C. (Z,Z,Z)-Allofarnesene [(2Z,42,6Z)-3,7,1 l-Trimethyl-2,4,6,10dodecatetraene] 170 (CI5H2J This is a component of the trail pheromone of the red imported fire ant (Solenopsis i n v i ~ r u ) . ~Williams '* et al. prepared 170 as shown in Scheme 567.7'8

16. lsoprenoid Hydrocarbons as Pheromones

277

wo Ph,P-CHMe

EGO

(22,42,6z)-im

Scheme 567

D. (Z,E)-Homofarneseneand (E,E)-Homofarnesene[ (3Z,6E)- and (3E,6E)-3,4,7,1l-Tetramethyl-l,3,6,lO-dodecatetraene] 171 and 172 (C1SH26)

These are the trail pheromone components of the red imported fire ant (Solenopsis i n v i c t ~ ) Alvarez . ~ ’ ~ et al. synthesized a mixture of 171 and 172 (Scheme 568).7’9Synthetic 171 and 172 had trail pheromone activity comparable to that of the natural pheromones (ca. 40 p g / ~ r n ) . ” ~

CH2C12 (30%)

HgCI,.CaCO, sq MeCN

0

(70% from A)

W

C

H

2) HPLC sepn

(80%)

O

Ph3P=CHZ

THF

>

(70%)

\

\

0

/

172

Ph,P=CH,

THF 171

Scheme 568

E. (E,E,E)-Neocembrene 173 (C20H32) This macrocyclic diterpene hydrocarbon is a termite trail pheromone of Nusutitermes exitosus, N. wulkeri, and N. g r ~ v e o l u s It. ~is~ also ~ produced in the

278

The Synthesis of Insect Pheromones, 1979-1989

>Q+Q

2) 1) SO2 LNH,iE$O chromatog.

6H (*).A

(34%)

OH

(*I-8 (55%)

OElNH2 -78%

>

16. Isoprenoid Hydrocarbons as Pheromones

279

Dufour's gland of fertile Queens of the Pharaoh's ant (Monomorium pharaonis), and it may serve as a Queen recognition pheromone.'" Kato et al. synthesized both the enantiomers of 173 by optical resolution of an intermediate (Scheme 569).722They employed menthoxyacetyl chloride as the resolving agent for (*)-A. (Incidentally, the absolute configuration given for menthoxyacetic acid in Ref. 722 is in error.) The resolved (+)-173 and (-)-173 showed pheromone activity of a high order, and they could not be differentiated from each other or from the racernic mixture in the bioassay. The activity recorded was of the same order as that of the natural pheromone. (R)(-)-(E,E,E)-neocembrene (173) was also synthesized by the asymmetric reduction of the ketone (&)-A with (+)-Chiraldm-lithium aluminum hydride complex to give (+)-B and (+)-C, the latter of which was further purified via D and deoxygenated, giving (R)-(-)-173 (Scheme 570).723

(t)-C

(54%)

(t).D. m.p.80°C [a)," +7i.4°(CHC4J

Scheme 570

[a],"

-1~O(cnci,)

280

The Synthesis of Insect Pheromones, 1979-1989

17. ISOPRENOID ALCOHOLS, FORMATE, ACETATES, PROPANOATES, AND EPOXIDE AS PHEROMONES

A. Sulcatol (6-Methyl-5-hepten-2-01) 174 (CBH160) This is the aggregation pheromone produced by the males of an ambrosia beetle (Gnathotrichus sulcatus) as a 65 : 35 mixture of (S)-and ( R ) - i ~ o m e r sIn . ~lab~~ oratory and field bioassays, G. sulcatus responded to sulcatol only when both enantiomers were present.725 Johnston and Slessor reported a synthesis of the enantiomers of 174, starting from the enantiomers of propylene oxide (Scheme 571).726They purified 174 as its crystalline p-nitrobenzoate.

rnp 54.55'~ [aloz t 6 1 .4"(CHC13

(95%)

(S)-174

lalo* +14.B0(E0H)

Scheme 571

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

281

Mori et al. employed biochemical methods for the preparation of (R)-174 and (S)-174 (Scheme 572).727*728 In the first approach, (S)-A was produced by

''a::% 0

i

/L COzEt

m.p. 38.539.OoC

(45% from A)

OH

1)DHP,TsOH 2)LU\IH,IEbO

jtCoZEt 3)TsCVC,H,N ($).A

(89%)

(100% e.e.)

46.1' (CHCI,)

Scheme 572

the reduction of ethyl acetoacetate with baker's yeast, the enantiomeric purity of which was 87% e.e.727They then devised methods to provide the pure enantiomers of A by employing Succharomyces bailii (yeast) and Zoogloeu rumigeru ( b a ~ t e r i a ) . ~ *Starting ~ ' ~ ' ~ from the pure enantiomers of A, the pure enantiomers of sulcatol were ~ynthesized."~

282

The Synthesis of Insect Pheromones, 1979-1989

Takano et al. started from ~-mannitol'~'and prepared the enantiomers of 174 via lactone A and the diol enantiomers B and B' (Scheme 573).73'They

D-Mannllol

(74% lrm B)

6'

= z u _j

(5)-174

[a], +13,9O(EIOH)

Scheme 573

developed another conversion of D-mannitol to (S)-sulcatol (174) (Scheme

574).732 In Takano's third synthesis of 174, microbial resolution of (+)-2,3dichloro-1 -propano1 was employed (Scheme 575).733 Biochemical methods were also employed for the synthesis of 174. Veschambre and his co-workers reduced 6-methyl-5-hepten-2-one with various mi-

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

/l+/Jon=z (S)-174

Scheme 574

E,,

Microbial resolution (40%)

'

CI

dil NaOH

EGO

>

(73%)

(Rb174 (91% e.e.)

Scheme 575

(RbA

283

284

The Synthesis of Insect Pheromones, 1979-1989

(S)-174 (94% ee)

Tkrmcmamobiwn brockii

\

(Qrdw) 24h (100%)

(S)-174 (29% ee)

Aspergilluc niger. 24h (80%)

(R)-174 (96% ee)

Scheme 576

croorganisms (Scheme 576),734 Saccharomyces cerevisiae and Thermoanaerobium brockii reduced the ketone to (S)-174,while Aspergillus niger gave (R)-174.734 Stokes and Oehlschlager resolved ( f)-sulcatol (174)with porcine pancreatic lipase and 2,2,2-trifluoroethyl laurate in ether (Scheme 577).735Wong

+

n.C,,H,CO,CH,CF,

0

Porcine panemarb lipasa (PPL)

in dty EGO r.1. 3 days

(S)-174 (97% e.e.)

(*).I74

Ester of (R)-174 (90% e.e.)

Scheme 577

et al. also resolved (f)-174with porcine pancreatic lipase and vinyl acetate.736 Maycock and his co-workers achieved a synthesis of (R)-174and (S)-174by using biochemical asymmetric reduction and the Barton decarboxylation reaction (Scheme 578).737

faloti4.8'

ONa 3)t-BUSH, A (71%)

/ LOH CO,EI

,*,

L& 2LDA

HO

(40%)

Scheme 578

(EIOH)

*u (R)-174 (a], -14 3 O (EtOH)

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

285

( f )-Sulcatol (174) was prepared from 4-phenylsulfonylbutanoic acid as shown in Scheme 579.738 0

1) 2n-BuU/ THF

-

'

OH

Na-Hg

HO -OH

S0,Ph

U

(76%)

O

H

(*)-I74

Scheme 579

B. Quadrilure [(3R,6E)-3-Acetoxy-7-methyl-6-nonene] 175 (C ,2H2202) Male square-necked grain beetles (Cathartus quadricollis) produce the aggregation pheromone 175,which is highly attractive to both sexes.739Only (R)-175 was biologically active.739 Kocieriski et al. announced a synthesis of (*)-I75 using the nickel-catalyzed coupling of methylmagnesium bromide with 2,6-diethyl-3,4-dihydro-2H-pyran (Scheme 580).740Johnston and Oehlschlager first prepared an (E,Z)-mixture of

(> 97% E)

(k1.175

Scheme 580

(f)-175,and then compared it with the natural pheromone by GLC as well as

'H NMR to confirm the E-geometry of the natural pheromone (Scheme 581).74' They then prepared ( f )-175 by the standard chain-extension reaction, treating an allylic acetate with an organocopper reagent (Scheme 58 Finally, both the enantiomers of 175 were synthesized by them from (S)-ethyloxirane (Scheme 582).74'The natural pheromone was shown to be (R)-175.Mori and Puapoom-

286

The Synthesis of Insect Pheromones, 1979-1989

48XHBr

1)

>

w40

ECHO 2)AC&YC,H5N

>

(*)-I75 ( E l = 3 1 )

DMF (50%)

1) LDPJTHF 2) Ac.pC5H,N

(89%)

2) H‘

>

(87%)

OAc

(*)-I75

Scheme 581

0 H

L M g C l , Cul

(S)-A

2) MCPBA

‘7pk’

1) k 2 C u UI E50

1) LDA I M F

a

2)H. 3) Ac20I C,H,N

(9175

(33% horn S)

OAC

1) MrCl I EbN,CH2CC

2)KOAclDMF

[a],,not reported.

& (Rb175

[abnot reponad Scheme 582

chareon efficiently synthesized (R)-175and (S)-175starting from the enantiomers of methyl 3-hydroxypentanoate (Scheme 583).742The key reaction was the cross-coupling between B-alkyl-9-BBN (A)and ( E ) -l-bromo-2-methyl-lbutene (B) dccording to S u z ~ k i and , ~ ~175 ~ was obtained in 34-35% overall yield in 8 steps.

C. (R)-3-Acetoxy-2,6-dimethyl-1,5-heptadiene 176 (C,,H,,02) This is the female-produced sex pheromone of the comstock mealybug (Pseudococcus comstocki) as isolated independently by Negishi et al .744 and Bierl-

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

287

1) LiOH

4C02Me

Me2Culi

(94%)

2 :E

-

1) Br, / CH2C12

Br 3) HCI (83%)

99.5 : 0.5

heat (73%)

mp 35,5-36,50c

B

(100% 2)

(S)-175

[ a 1 , ~ ~ . (CHCI,) 05~

dppl s 1, i'-bis(dipheny1phosphino)lenocene

Scheme 583

Leonhardt et a1.745To confirm the proposed structure, Uchida et al. prepared (f)-176 as shown in Scheme 584.746Bierl-Leonhardt et al. also synthesized

+

LirrHF &Bf

(11.4%)

,

Ac20/C5H5N

(7w

OH

OAc

(f)-i76

Scheme 584

(+)-176 (Scheme 585).745Baeckstrom et al. prepared (f)-176 via photooxi-

1) AI(OPi)@.mw.

heat

2) AcpC,H5N

OAc (*)-1,76

Scheme 585

dation of 2,6-dimethyl-2,5-heptadiene,which was obtained by cross-coupling of lithium bis(2-methylpropeny1)cuprate with 3-methyl-1-bromo-2-butene (Scheme 586).747Langlois and his co-workers achieved a synthesis of (f)-176 via a sila-Cope elimination (Scheme 587).748The overall yield was 20%. Skattebdl and Stenstrdm synthesized (f)-176 in three steps from methyl chloroacetate and methyl acrylate (Scheme 588).749Scheme 589 illustrates the synthesis

The Synthesis of Insect Pheromones, 1979-1989

288

hv, O,, Rose Bangal

(n-Bu),NBH,. CHC,! (10.9%)

Scheme 586

B

A

( 1

: 1 )

C

MeCN 80°C (90%)

OAC

3) Ac,O/C,H,N

(f)-176

(77%)

Scheme 587

(74%)

(f)-176

Scheme 588

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

289

Scheme 589

of (+)-176by Ishchenko et a1.750Cohen's synthesis of (f)-176(Scheme 590) proceeded in 47% overall yield.75'

1) CeCI,, - 7 8 ' ~

&

SPh

.U

& ,kcHo

THF, -78OC

-2)

nMEDA

3) Ac,O/C,H,N

(47% overall)

OAc (&)-I76

Scheme 590

The dextrorotatory [[a],, + 6.2"(hexane)] natural pheromone745was shown to be with R-configuration by the synthesis of (R)-176and (S)-176by Mori and Ueda (Scheme 591).752The Sharpless asymmetric epoxidation was used for the

[alDn+5.68' (hexane) (90% e.e.)

(S)-176

(a],p

Scheme 591

-5.72' (hexme) (91% e.e.)

The Synthesis of Insect Pheromones, 1979-1989

290

introduction of asymmetry to prepare (R)-176 and (S)-176752or (R)-176 (Scheme The R-configuration of the natural pheromone was confirmed by its

1) TsCl/ C,H,N

A%

2) Nal I M,CO (69%)

(76%)

'

li(OPr'),, (+)-DIPT t.Bv00H / CH,CI, -2OOC (Repeatedtwice)

OH

(22%)

(81%) . .

OH [aIon+31 .B0 (hexane) (96% em)

OAc (R)-178

l r ~ ] ~ ~ + 4(hexane) .35~

Scheme 592

derivation from (S)-phenylalanine (Scheme 593).753The key-intermediate A in

AI(OPi), toluene

heat

'

(R)-176

6H (R)-almhol

[a]d't7.8lo (hexane) (18.6% e x . )

Scheme 593

this conversion was prepared from (S)-phenylalanine in six steps according to the method of Terashima et Partial racemization took place in the course of the conversion to yield (R)-176 of rather low enantiomeric purity. Larchev&queand Petit achieved a synthesis of (R)-176 starting from @)-seine (Scheme 594) .'55

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

Ph,P-CH, SO, chromatog (5G%)

> y q :;;>A+ heat

*

OH [a]olo+28.30(hexane) (>Qi% e.e.)

291

/LA 6Ac (R)-176

(a]020+7.00 (hexane)

Scheme 594

D. Neryl Formate [(Z)-3,7-Dimethyl-t,Coctadienyl Formate] 177 (CIIHl802) This is the alarm pheromone of the mold mite (Tyrophagus putrescenriae) and was synthesized by treating nerol with acetic fotmic anhydride (Scheme 595).756

.

.

Scheme 595

E. 7-Methyl-3-methylene-7-octenyl Propanoate 178 (C I 3H22OJ, (2)-3,7-Dimethyl-2,7-octadienyl Propanoate 179 (C 13H2202), and (E)-3,7-Dimethyl-2,7-octadienylPropanoate 180 (C 13H2202) The San Jose scale (Quadraspidiotus perniciosus) is a major and widespread .orchard pest. Its female-produced sex pheromone is a mixture of 178 (48.5%), 179 (46.7%), and 180 (4.8%).757-758 Anderson et al. synthesized both 178 (Scheme 596) and 179 (Scheme 597) by the application of organocopper chemi s t ~ - ~Each . ’ ~ ~synthetic component (178 or 179) was independently attractive to male San Jose scale. Synthesis of 180 was also achieved by Anderson et al. again by means of organocopper chemistry (Scheme 598).758This component

292

The Synthesis of Insect Pheromones, 1979-1989

(70%)

1) CuW Me,S

(EICO),O

2) =O -SM I e3

C5H6N

(45% from A)

3) HCI aq %OH

Scheme 596

(180) was individually attractive like the other two, and there did not appear to be a synergistic effect on trap catch when a mixture of components was used as a lure.758In Weiler's synthesis of 178 (Scheme 599), 179, and 180 (Scheme

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

293

178

Scheme 600

600), a P-keto ester served as the common i n t e ~ m e d i a t e . 'Szrintay ~~ and coworkers developed a concise synthesis of both 179 and 180 (Scheme 601), start-

.

Netyl propanoale

.

I-BUOCI

~

~ Geranyl propanoale

sio, / b x a n e (82%)

179

> O+moE1 CI

E

NaBH,. DMFLii (59%)

'

A - L O C O E I

~

180

Scheme 601

ing from the commercially available monoterpenes, nerol and gerani01.'~' Ferroud et al. prepared 180 by employing bis(p-tolylsulfony1)methane as the building block (Scheme 602).558Lombard0 and Weedon prepared 178 by a

Scheme 602

photochemical deconjugation reaction (Scheme 603) as a mixture with two other products.762 A lengthy synthesis of 180 was reported by Dhokte and Rao (Scheme 604) starting from methyl l e v ~ l i n a t e . ' Odinokov ~~ et al. synthesized

294

The Synthesis of Insect Pheromones, 1979-1989

2.7

178

:

1 .o

1.8

Scheme 603

L C 0 , h k

-

1) HOCH,CH,OH,

TSOH/C5H5

PCC. NaOAo

2) LIAIH,

0

n 0 0

n

0

II

(EIO),P CHMeC0,EI

%CHO

NaH / E$O

CH,CI,

(91%)

(86%)

n

o U C O z E t

H, / Pd-C MeOH

n O

>

U

O

H

1)dil HCI

>

2) TsCl / CH ,N ,

(93%)

(eex)

(8%)

0

180 from geranyl propanoate (Scheme 605).7" Moiseenkov et al. also prepared 179 and 180 (Scheme 606).765 F. Ipsenol (2-Methyl-6-methylene-7-octen-4-ol) 181 (CloH180) and Ipsdienol (2-Methyl-6-methylene-2,7-octadien-4-ol) 182 (CloH160) (S)-( -)-Ipsenol (181) and (S)-( +)-ipsdienol (182) were first isolated as the pheromone components of the California fivespined ips (Ips puracanfusus). In

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

295

(62%)

eAcOK

*OCOEI WZS+c10,-

aq EtOH 180

(20%)

Scheme 605

.

. (74%)

(74%)

Scheme 606

California, the male pine engraver (Ipspini) produces (R)-(-)-182 as the major aggregation pheromone, and this enantiomer was found to inhibit the attractive . ~ ~ ~+)-Ipsdienol (182) intempted pheromone response in I . p ~ r u c o n f i s u s (S)-( the response of the Californian I. pini to (I?)-( - ) - ~ 2 . ~On~ the ' East coast of

296

The Synthesis of Insect Pheromones, 1979-1989

the U.S.A., I. pini reacts to (S)-(+)-182. This interesting phenomenon was studied at the receptor cell level by electrophysiological method to reveal the existence of two distinct types of receptor cells: one keyed to (+)-182 and the other keyed to ( -)-182.768 Further detailed study on interpopulation and intrapopulation variation of the enantiomeric purity of 182 in 1. pini was reported by Miller et A mixture of verbenone and ipsenol inhibits the attraction to the aggregation pheromone as emitted by eight-toothed engraver beetle (spruce bark beetle, Z. typographus), while that of verbenone and ipsdienol attracts the insects.770 Over 10 different syntheses of (+)-181 andlor (+)-182 have been reported since 1979. Cazes et al. synthesized (f)-181 in 52% overall yield (Scheme 607).77'A synthesis of (+)-182 was reported by Cheskis et al. (Scheme 608).772

1

0

(f)- l e i Scheme 607

(f)- 182

Scheme 608

Masaki et al. converted myrcene to (k)-l 82 via the addition of benzenesulfenyl chloride (Scheme 609).773*774 Snider and Rodini prepared (f)-181 in a single step from isoprene and 3-methylbutanal by an ene reaction (Scheme 610).775 The major product of this reaction, however, was the Diel-Alder adduct, and (f)-181 was a minor product. (+)-Ipsenol (181) was synthesized by Wilson et al., employing 2-trimethylsilylmethylenecyclobutane as an isoprene equivalent (Scheme 61 l).776 Halazy and Krief prepared ( + ) - l S l by using cu-selenocyclobutyllithium as a 2-lithio-l,3-diene equivalent (Scheme 612).777Sakurai et al. synthesized (It)-lSl and (+)-182 starting from 2-trimethylsilylmethyl-l,3-b~-

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

~ 4 -0ACOH

OAc

Scheme 609

(f) - 181 (16%)

25%

Scheme 610

f

1)n-BuLi/TMEDA-hexane

SiMe,

2) Me,SiCi

,

TiCI,


15OoC)

LCHCJ

(f).I81

(86%)

Scheme 61 1

nnx

heal (150OC)

(wan$

'

(f)- 181

Scheme 612

(50% overall yield)

297

The Synthesis of Insect Pheromones, 1979-1989

298

Scheme 613

tadiene (Scheme 613).778The same silyldiene, when treated with tetra-n-butylammonium fluoride, efficiently isoprenylated aldehydes to give (f)-181and (f)-182(Scheme 614).779Rousseau and Drouin used allylic organozinc com-

(f)- 181

+

A C H O

(n.Bu),NF / THF

SiMe,

S°C,2h

(f) .I82

Scheme 614

pounds for the conversion of the nitriles to the ketones corresponding to (f)-181 and (f)-182(Scheme 615).'" A dienylborane A was prepared by Bubnov and

ACN +

& S S o ,

o aTHF (Ag)

>

(70%) 2) chromalog.

u

w

z 3

[+ '

+so* 7

) 18ooc_-

I

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

2Y9

Etinger, and was used for isoprenylation of the aldehydes to produce ( + ) - l S l and (&)-I82quite efficiently (Scheme 616).78' Semmelhack and Fewkes used

(75%)

A

(q4-isoprene)iron tricarbonyl as the isoprene equivalent and synthesized (+)-181 and (+)-182 (Scheme 617).782Vorskanyan et al. published an additional syn-

Fe(CO),

basffiH202

(QlK)

> (*)-la2

Scheme 617

thesis of (*)-181 (Scheme 618),783 which is a variant of the previous synthesis

(*)-re1

Scheme 618

300

The Synthesis of Insect Pheromones, 1979-1989

by Cheskis and Moiseenkov (Scheme 619).784A new route to (+)-181 was

Scheme 619

(*).I81

developed using 3-methylene-2,3-dihydrothiopheneS,S-dioxide as an allylic sulfone and Michael acceptor (Scheme 620).785Brown and Randad synthesized

E5N or K,CO,

NO, ____j

HN=C(NMe,), MeCN (50%)

CH,CI,

zi

'

(500A)

NaHCO, CDCI, 125'C. 3h

(*)-la1

Scheme 620

(+)-181 and (+)-182 by using B-isoprenyl-9-BBN in a manner similar to Bubnov7" (Scheme 62 l).786

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

301

Six new papers have appeared since 1979 on the preparation of the enantiomers of 181 and 182. Baeckstrom et al. employed myrcene as the starting material, prepared (f)-182first (Scheme 622), and then obtained (R)-(-)-182

-

(150sec) (87%)

3U4NBH4

KOH

MeOH (95%)

H

(*).re2

U pee' CH,CI, (43%)

HCI

>-

~

A

-lOO°C. THF (70%)

(R)-182

1 a lon'

-7.0°(MeOH)

(63%e.e.)

Scheme 622

(63 % e.e.) by Noyori's asymmetric reduction of the corresponding ketone A.787 Kubo et al. carried out the optical resolution of (f)-181and (+)-182after their derivatization with (R)-(+)-a-methoxy-a-trifluoromethylphenylacetic acid (MTPA) to the corresponding MTPA esters, followed by HPLC separation of the d i a s t e r e ~ m e r s . 'H. ~ ~ Yamamoto and co-workers prepared (S)-181of > 99% e.e. by their new asymmetric reaction using chiral allenyl boronic ester (Scheme 623).789

302

The Synthesis of Insect Pheromones, 1979-1989

Brown and Randad employed B-isoprenyldiisopinocampheylboraneto prepare the enantiomers of both 181 and 182 (Scheme 624).786.790 Bubnov modi-

(l%e.e.)

2) W H O

$*“OH

$OH

2)MeCHO 3)(HOCH,),NH

3)(HOCHZ),NH

(60%)

W182

lal,n+i3.20(MeOH) (96% e.e.1

(R)-l82 talon -i3.1°(MeOH) (%% e.e.)

Scheme 624

fied his synthesis of (f)-181 and (+_)-182via organoboron intermediates to prepare the enantiomers of both 181 and 182.791A unique synthesis of (R)-182 was reported by Franck-Neumann et al., who used an optically active iron complex A as the key-intermediate (Scheme 625).792However, (R)-182 was the minor product of this synthesis.

p

“K2? >

2) HPLC sepn.

p p +

FGO),

(R)-182

1 al0 -13’ (90%e.e.)

( 2 :3)

Isomer

Scheme 625

(9:i) chromalog. sepn.

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

303

Mori and Takikawa prepared both the enantiomers of ipsdienol(l82) starting from the enantiomers of serine (Scheme 626).793The key-step was the epoxide opening of A with a Grignard reagent prepared from chlorogrene. 1) H&,NaNO, HOYCoZH NHa 2) KOW MeOH (S).Serine

,.g' >COzK

CO,Me

Mez=,

A

1hrown4

(53%)

(78%)

-

A CuEf M e p T H F (66%)

1) (i-Bu)glH

OTBS

-

2) (72%)

(R)<-)-IeZ [ a l~7.15.30(MeOH) (296% e.e.) Similarly:

HOYCozH

NHz (R).Serine

___j

(S)-(+).182

[a

t15.7°(MBOH)

(296% e.e.)

Scheme 626

G. Grandisol (cis-2-Isopropenyl-1-methylcyclobutaneethano1) 183 (CIOH

1K0)

(1R,2S)-( +)-Grandis01 (183) was first identified as a pheromone component of the male cotton boll weevil (Anrhonornus grandis). It was also shown to be a pheromone component of the bark beetle (Pityophihorus pityographus).7y4 Over a dozen syntheses of (39-183 or (+)-183have been recorded since 1979, in addition to 15 syntheses reviewed in Ref. 1. Rosini et al. reported a short synthesis of keto acid B from the known bicyclic ketone A (Scheme 627).795The acid B had previously been converted to (+)-183. Negishi's syn-

"+* QT;>QH-l.-+[+%] 0

KMnO,,KH,PO,/YI,O

C,,H,(n-B

(85%)

U),P 'K'CH2CL

(7%)

(94%)

p[ (fM

+ Q ]

(*Pa

'=

7

:

(*).I83

Scheme 627

3

304

The Synthesis of Insect Pheromones, 1979-1989

thesis of (5)-183 was achieved by using his silicon-promoted cyclization reaction of w-haloalkenylaluminum as catalyzed by zirconocene (Scheme 628).796*797 The final product of this synthesis was a mixture of (+)-183 and

its rrans-isomer. Photo-induced rearrangement of ( +)-A2-carene (A) to a bicyclo[3.2.0]heptene B was used by Sonawane et al. (Scheme 629)798for the

(*I4

Scheme 629

preparation of ketone C, which had been used by others in the synthesis of (&)-183.Another inefficient synthesis of the ketone C from E was reported by Rdmming et In Rosini's synthesis of (*)-I83 (Scheme 630), the key-step

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

305

0

&CO,El

6

(85%)

hv CuOTV E $ 0 (95%)

HMPA

L '\

i)Me,SICH,MgCVTHF 2) SOC12 3) 40

heat

#

@+

(94%)

-

(88%)

:

(ah)

7

(f). 183

(75%)

*ozH

/

(87%)

ecozH :T 6 3

MeMaV EL0

+

3) cm,

/

OH

Scheme 630

was the photocyclization of 3,6-dimethyl- 1,6-heptadien-3-01.~~~ The overall yield of (f)-183 by this synthesis was 3 1 % from methallyl chloride. Rosini et al. further improved their photocyclization route (Scheme 63 1).80' In this case, too, the photocyclization step (A -P B) resulted in an excellent yield.

%1) Me,SiCH,MgCV

3) 2)AcCI LIAIH,

E$O

<Mg

A

E P (7%)

(em)

l)PCI$EhO 3) H30' (*).la3

Scheme 631

X

C

H

O

+

CI

306

The Synthesis of Insect Pheromones, 1979-1989

+

A very short synthesis of (+)-183 by Dreiding et al. utilized [2 2lcycloaddition of dichloroketene to construct the cyclobutane ring (Scheme 632).802 There is a drawback at step C D because other byproducts (E, F, +

c'3ccoc',

1) M e p o 300/aq.NaOH

A m $ :'

Zn-Cu/ E$O

CI

z(63% from ~ A) >

A

A

~

E5oN'Cr

B

E

q o 2) Repealed chromalog.

(34%)

F

0

Scheme 632

and G ) had to be removed by repeated chromatography. Kim et al. used intramolecular alkylation to build up the cyclobutane ring (Scheme 633).803 This 1) MeCH,C(OEI), 1) PhCOCU C,H,N

3) NaEH,

PhOH.heal 165OC 3) TsCI.DMAP/ CH2CI,

reaction unfortunately furnished the unwanted trans-compound A as the major product, while the desired ester B was the minor product. Kametani et al. employed benzobutane B, which was prepared from p-methoxybenzaldehyde,8@' as the starting material for the synthesis of (+)-183 (Scheme 634).805Conversion of B to C was the crucial feature of this route which, however, was too lengthy. Grandguillot and Rouessac prepared (+)-183 by a ketiminium [2 + 2lcycloaddition (Scheme 635).806

1) NY liq.NH3,MeOH

NC

CH,CH,CN

.

Me,CuLi E120 (83%)

OJ $

l)LOA.Me,SiCI

>

>

2) Pd(OAc)Z/MeCN (+).

(6596)

c

0

(78%)

1) Me,CuW EbO

2) Ac,O

H

(81%)

Scheme 634

boooh 1) ZnCI,,

CI

2) bask hydrdysis

13

7

1) CAN,MeCNaq

2) SO, chromalog.

(*)-re3

Scheme 635

307

The Synthesis of Insect Pheromones, 1979-1989

308

Six new syntheses of the enantiomers of 183 have been published since 1979; two by optical resolution, two by biochemical asymmetric synthesis, and two by chemical asymmetric synthesis. Webster and Silverstein resolved a bicyclo[4.2.O]octanecarboxylic acid C (Scheme 636) in analogy with Mori’s 1978 work, in which a similar bicyclo[3.2. I]heptanecarboxylic acid was resolved (Scheme 233a, Ref. I).*’’ For the cleavage of the amide bond of D’ and D”, they developed a new procedure as shown in Scheme 636.Cf.808 No direct proof 0

,hv

CH,=CH,

bCOzMe A

) : : :

2) KOH I aq W

’

2) (5)u-phenethylamine

H

.TsOH / C,H6

(62%)

(56%)

sepn

u

U D

U

more polar D‘

less polar D’

(37%)

(41%)

1) LiAIH, I EbO D’

2) TsCl/ CH ,N ,

I ) Li / NH,, eq THF

3) L i E p H heal (82%)

-

(64%)

u

1) PhSeCl/ EIOAc

RuO, - NalO, CCI, / aq MeCN’

3)H,O,/CH,CI,-C,H,N

4) EbO/ N-HCI

(45%)

Similarly: D”

1) Ph,P=CH,/THF 2) LiAIH, (48%)

3 4 (1S,2R)-183

[u],2’

(1R,2S)-183

-18.1°(n.hexans)

[alDT” r18.4’ (mhexane)

Scheme 636

was given in this paper to support the claimed > 99% enantiomeric purity of the enantiomers of 183. Mori and Nagano modified the Dreiding synthesis of (f)-183 (Scheme 632) to furnish both the enantiomers as shown in Scheme 637.809 They resolved alcohol ( f ) - B by acylating it with (-)-w-camphanyl

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

( iWo de )

Similarly:

' , ' : ) a [

(1R,2S)-183 +22.1' (hexane)

-

309

(1Wde)

(1S,2R)-183 [a],2',0 -17.7' (hexsne)

Scheme 637

chloride. The resulting diastereomers C and C' were separable by chromatography. In spite of the small discrepancy between the [a],, value of their (+)-183 and that of (-)-183, their enantiomers proved to be enantiomerically pure by examining the 'H NMR spectra (400 MHz) of their MTPA esters.Cf.8" The rotation value is not always a good criterion to judge optical purity. Chiral building blocks generated by biochemical means were used by two groups to prepare 183. Jones et al. obtained lactone B by oxidizing meso-diol A with horse liver alcohol dehydrogenase (HLADH) and converted B to (+)-183 (Scheme 638).*1° The enantiomeric purity of their (+)-183 was estimated to be ca. 100% by ' H NMR examination (100 MHz) of its MTPA ester in the presence of Eu(fod)3. The final step of their synthesis, however, was not selective, and GLC separation of the products was necessary to secure pure 183. Mori and Miyake synthesized the enantiomers of grandisol (Scheme 639) starting from ethyl (R)-3-hydroxyb~tanoate.~' ' The starting material could readily be prepared by ethanolysis of PHB (poly-0-hydroxybutyrate) of microbial origin. The key-step was the intramolecular cycloaddition of the acyl chloride A to give a diastereomeric mixture of C and D via ketene B. Separation of the mixture was successful after reduction to give pure E and F. These were converted to (+)-183 and (-)-183 via G and H. Careful estimation of the enantiomeric purity was executed at the stage of the ketones C and D, and also with the final products. 'H NMR studies on the MTPA esters of (+)-183 and (-)-183 at 400 MHz proved their 100% enantiomeric purities. The enantiomers of 183 synthesized by Mori and Miyake were assayed by Dickens against the boll wee-

310

The Synthesis of Insect Pheromones, 1979-1989

Y.yield) . . . [alOz5 +14.8’ (hexanel

...

mp64-S5°C

Scheme 638

vil. He found only (1R,2S)-( +)-183 to be bioactive by EAG studies and field This was not in accord with the old data, which show both (+)-183 and (-)-183 to be bioactive in laboratory bioassay against the boll In the old experiments, (+)-183 of 80% e.e. and (-)-183 of 91% e.e. were used. This rather low enantiomeric purity of the samples and/or the design of the bioassay must have been the origin of the previous erratic result. The following two asymmetric syntheses of 183 employed, as the key-steps, intramolecular photocycloaddition of alkenes to chiral a,P-unsaturated carbonyl compounds. First, Meyers and Fleming developed asymmetric [2 21 photocycloaddition of ethylene to a,@-unsaturated lactam A to give B (Scheme 64O)?I4 The lactam A was prepared from (8-valinol and levulinic acid. The product B was contaminated with ca. 7-8% of its endo-cyclobutane-fused isomer. Because the photocycloaddition mixture was further processed without separation, the resulting (-)-grandis01 (183) was enantiomerically impure (ca. 88% e.e.). Second, Demuth et al. prepared both (+)-183 and (-)-183 by asymmetric photocycloaddition of 2-methylcyclobutene to optically pure spirocyclic enone A (Scheme 641).8’5The spirocyclic enone A could be prepared from (-)-menthone and r-butyl acetoacetate. This is the shortest enantioselective synthesis of grandisol enantiomers.

+

(COCI),.DMSO EfN / CH,CI,

-oq:

1) LiB(s-Bu),H / THF

C (10% e.e.)

C

1

F

D

=c

(73%)

Similarly:

ti

(1S,2R).180 -20.0' (hexane)

[alon.'

5

02H

(S)-Valinol

5% H,SO,-MeOH heal

0

N2H,.KOH (96%)

H ' s

(56%)

B

1) TsCl C,H$ 2) NnCN / HMPA

(62%)

0

D (IWhe.e.)

'

H

(tR,2S).183

m.p. w.550.9%

[a]?'

+20.So (hexane) 100%

8.8.

.1W%e.e

Scheme 639

-H,O

1)s-BuLi/THF.Mel

(80%)

2) 8-BuLi/ THF.Ph,Se, 3) H,O,. CH ,N ,

q;Me [ $'F ]

,%++

+

C

"?;;""

Ph,P=CH, THF

(W%)

H

I

(45 :55)

1) (i-Bu)$IH

Z)LiAlH,

(63%)

0

A

(62%)

'

'%

hv CH2~CHz~CHzCb PhCOMe.-7a°C (93%)

LiAIH,/THF

(96%)

D

> (tS,2R).183 (hexane)

[alo -16Lt2'

BB% e.e.

Scheme 640 311

312

The Synthesis of Insect Pheromones, 1979-1989

H. (1R,3R)-3-IsopropenyI-2,2-dimethylcyclobutanemethyl Acetate 184 (C12H2002)

The female-produced sex pheromone of the citrus mealybug (Plunococcus cirri) was identified as 184 by Bierl-Leonhardt et a1.816Their synthesis of 184 (Scheme 642) was achieved by the photolysis of (+)-cis-verbanone to give olefinic al-

67

&o o;;+ L.. ONaEH4

(t)-a-Pinene

(

+ )cQ.Vetbanone

2) A$O/ C,H,N

A

P

,

,W'

( 1R. 3R )-184

+148O (CCI,)

natural pheromone :

[al,la25+ 1 6 8 O (CCI,)

Scheme 642

dehyde A, reduction and acetylation of which furnished the pheromone.816 (lS,3S)-Isomer of 184 as well as the trans-isomer and the alcohol precursor of 184 were far less active than ( 1R,3R)-184.8'6Gaoni synthesized (f)-184by conjugate addition of isopropenylmagnesium bromide in the presence of copper(1) bromide to I-benzenesulfonyl-2,2-dimethylbicyclobutane(Scheme 643).8'7The bicyclobutane was prepared from a y,6-epoxysulfone.818The final purification of (f)-184was carried out by preparative GLC. Carlsen and Odden's synthesis of 184 started from (+)-verbenone, which was oxidized with ruthenium tetroxide (Scheme 644).8'9Starting from (+)-a-pinene, Odinkov et al. synthesized 184 as shown in Scheme 645.820A four-step synthesis of 184

17. lsoprenoid Alcohols, Forrnate, Acetates, Propanoates, and Epoxides

313

(47.51% I

1)

(2

(*).I84

Scheme 643

I)O,/MeOH 2) H, / Pd.CaC0,-PbO ( 99 (+)a.Pinene

Me

'CHo

A50 EbN (66%)

Ph,P=CH,

+

Me0

'p".

c

2 M

THF

,

')o,/sio~

AcO7

,

Me0

2) TsOH / MeOH

1) PPTS / Me,CO 2) ( i.Bu)#H

O M

(03% )

314

The Synthesis of Insect Pheromones, 1979-1989

6

was reported by Wolk et al. starting from (+)-a-pinene (Scheme 646).82'Out KMnO,~(N*,),~O,>\pbO

y o

(+)sl-Pinme

H20 ( 87% )

;,,I

~

CCI,

W2H

'F$.

F

Me,NOAc/DMF

>

( 63% )

(65%)

( 9241e.e.)

P;H ,,

,V*'

~

( 71%)

(1R,3R)-184 [a]:' +19.B0 (CHCI,)

(280%8.8. 1

Scheme 646

of eight analogs of 184, only (1R,3R)-3-isopropenyl-2,2-dimethylcyclobutaneethyl acetate was bioactive, showing that all functional groups of 184 are essential for optimal biological activity.822 Serebryakov et al. prepared 184 essentially in the same manner as employed by Bierl-Leonhardt (Scheme 647).823

Scheme 647

Barton employed his radical decarboxylation reaction to prepare 184 as shown in Scheme 648.824

) :;:;

1) Ph,SbS &MeC,H,),

-(

CHlCh r.1.

Ph,P-CH,

( 75% )

'

L

O

A

o

(lR,3R)-lW

Scheme 648

0,

>~

O

I a], +lo2 f3'

A (CHCI,)

C

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

315

I. Seudenol (3-Methyl-2-cyclohexen-1-01)185 (C,H ,20) This is a component of the aggregation pheromone produced by the female Douglas-fir beetle (Dendroctonus pseudotsugae). Since Mori's synthesis of the enantiomers of 185 (Scheme 235, Ref. I ) , three papers have appeared on the enantioselective synthesis of 185. Noyori and his co-workers developed a new method for kinetic resolution of racemic allylic alcohols by BINAP-ruthenium(I1)-catalyzed hydrogenation and obtained (S)-185 (Scheme 649).825Two

.

H, / MeOH

&-(+ &)

4alm. 26%. SGU (46%recovery) subsbate I catalysl mde ratio 690

-

Scheme 649

papers on the synthesis of optically active 185 were reported based on enzymatic resolution. Wong et al. employed lipase of the Pseudomonas species (Scheme 650),736while Mori and Ogoche employed pig liver esterase (Scheme 651).826

..

[alDn+la3' (CHCI,) -26.7' (CHCI,) ( 61.8% ) (205%) ( 29% e 8. )

(32% conversion )

Lipase hom Pseudommassp. H,O, pH 7 phosphatebulfer (R)-acetete

[

( 59% conversion)

alon tt38.3' (CHCI,)

(R)-185

92% e.e.

Scheme 650

[ale IWIrepaned

The Synthesis of Insect Pheromones, 1979-1989

316

&

(+).Amtale

(30 9)

pig liver esterse 2G%MeOH

( S j.185

O.lM phosphate bulfer pH 7.5, .IO°C. 72hr ( 25% mnvemion )

1) AcPO/ C,H,N

/

[ulon 40' (CHC13)

23% MeOH, pH 7.5

( 75% wnversion )

(slop

( R )-amlate +22.0 (CHCI3)

laIon

/

20% MeOH, pH 7.5 ( 50% convarsion )

(R)-185

(S)-I85 .93.0

( 22.38

'

'(CHCl3)

+R.O (CHCI~) ( 4.08

( 3.0g)

J. 1-Methyl-2-cyclohexen-1-01 186 (C7H,20) This is the component of the female-produced aggregation pheromone of the Douglas-fir beetle (Dendroctonuspseudotsugae) that attracts both sexes, males p r e d o r n i r ~ a n t l yOptically .~~~ active 186 was synthesized by two groups. Posner's synthesis started from chiral sulfoxide A (Scheme 652),x28while Mori et al. converted optically active seudenol (185) to 186 (Scheme 653).826*x29 Both of the syntheses were based on the intramolecular transfer of chirality.

0 82% d e.

A

Can be purified by chromalog

Scheme 652

(5)-18%

[ a lon

IaJDn-76,5O(EbO)

t75.8' ( ~ $ 0 )

Scheme 653

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

317

K. (Z)-2-Ochtoden-l-ol [(Z)-3,3-Dimethyl-A'i~-cyclohexaneethanoI] 187 (CIOHIBO)

This is a component of the male-produced sex pheromone of the boll weevil (Anthonornus grandis). Masaki et at. examined the acid-catalyzed cyclization of the terminally functionalized myrcene derivatives (Scheme 654) and obtained

@

phs-r;l'

-2OOC

A

,

PhSCl CH,C,, (

b

'E;?

>

p h s $ ~ ' a o A c ' 2) D ~SO,, ( 58%chromatog. horn A ) phs B

-XlOC CHO

E : Z = 75 '25

0 i)TsNHNH,/MeOH

MCPBA

-A

0

187

L 87% )

Scheme 654

E:2=87:13

187.830.83I The major product, however, was the E-isomer of 187. Mori and Itou modified Masaki's procedure to prepare geometrically pure 187 (Scheme 655).832Thus, purification of A by medium pressure liquid chromatography

0 -20

-

PCC / CH,CI,

-30 OC

KOH ( 90%

1

The Synthesis of Insect Pheromones, 1979-1989

318

resulted in the separation of (E)-A and (2)-A, the latter being converted to 187. Because (2)-A was the minor product, conversion of the E-isomer to 187 was executed by the olefin inversion (Scheme 655).832

L. (E)-3,7-Dimethyl-2-octene-1,8-diol 188 (Ci O H 2 0 0 2 ) This is one of the components of the hairpencil secretion of the African monarch butterfly (Danaus chrysippus). Since 1979, four syntheses of (*)-lSS and a synthesis of (S)-188, as well as that of (R)-l88 of low e.e., have been reported. The absolute configuration of the natural 188 has yet to be determined. Fujisawa's synthesis of (+)-188 employed the ring-opening reaction of a-methyl-P-propiolactone as the key-step (Scheme 656).833The final product I -Ph,SiOV;O ~02~'

Cul/ THF-Me,S

2) dil HCI

I xylene

polymeric cataiyst,hsat

'

(82%)

(87%)

AIH, (89%) / THF

OHCUCOM ,e

I

HO& .,-& , OH ( f ) - l 8 8 (E 2 4 1 )

Scheme 656

by this synthesis was a mixture of 188 and its 2-isomer. Copper-catalyzed substitution of an allylic phenylsulfone with a Grignard reagent was the key-step in Julia's synthesis of (f)-188 (Scheme 657).834Julia also prepared optically

A

3) dil HCI

\

(89%)

2) H202-NaOHaq 3) dil HCI

(fl)-lBB = t2.2' (&bent not spalied.)

la],"

( m m %e.e.7)

Scheme 657

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

319

active 188 by asymmetric hydroboration of the olefinic intermediate A.834Ferroud et al. synthesized (f)-l88 by employing bis(p-tolylsulfonyl)methane as an initial building block (Scheme 658).558Dhokte and Rao's synthesis of NaCH(S02+-

-QSoz

),

PdoZ/THF -&so,

'&OH

(70%)

i

+SiCl,lrnidarcle/

1)

*OH

')

&WO,E(

DMF

, Pd(dp2

-Q-SOa

(80%)

(8Ph)

Scheme 658

(f)-188 started from methyl levulinate and proceeded in the conventional manner (Scheme 659).763Gramatica et al. used baker's yeast to prepare (S)-188 of high enantiomeric purity (Scheme 660).835 I)

0

rz~

O W

n

,TsOH/CBH,

h C O , M e

~

11

I

HZ/ Pd-C

(EQ),PCHCO,EI C

H

>

NaH/EbO O

(91%)

3) PCC,NaOAc/ CH,CI,

o b C O z E t

(91%)

n

(76%)

(86%)

2) prep HPLC

Scheme 659

1) Ac,O I C,H,N

2)Se02/EtOH (36%)

*OH

1) bakets yeas1

,

2)KOH.EIOH

u

LiAIH, O

U

C

0

>

3) siO,-AgNO, chromalog. (20%)

2) NaCN.Mn0, AcOH.MeOH

(S)-l88 -9.1'(CHCI,) (>97%ee)

2) Si0,-AgNO, chromalog.H

I ) baker's yeas1

>

2

W

>

(82%)

(35%)

Scheme 660

HO

C

O

,

M

e

UOH ..

IS)-108 [a]?

(CHCI,)

The Synthesis of Insect Pheromones, 1979-1989

320

M. (2E,6E)-3,7-Dimethyl-2,6-decadiene-l ,lO-diol 189 (C 12H2202) This is one of the components of the hairpencil secretion of the male Queen butterfly (Danaus gilippus berenice). Masaki et al. synthesized 189 (contaminated with 11 % of its 6Z-isomer), starting from geraniol (Scheme 661).836

1.2eq I-BuOK

THF-OMSO O°C.2hr

>

Raney-Ni M e O Z C H ~ O C H z P h

M

e

(82%)

O

,

C

~

O

C

H

,

P

8E:62=89:11

(72%)

1) LiAIH, /EGO

OH 188 (6E:BZSBQ:lt)

(68%)

Scheme 661

N. (3S,6R)-3-MethyI-6-isopropenyl-9-decenyl Acetate 190 (C,,H2,02) and (R,Z)-3-Methyl-6-isopropenyI-3,9-decadienyl Acetate 191

(c16H2602)

These are the pheromone components of the female California red scale (Aonidiella aurantii). Anderson et al. determined the absolute configuration of 190 as 3S,6R in the following manner.837 First, a mixture of all four diastereomers of 190 was prepared from (+)-citronello1 in four steps (Scheme 662);

2) 1) MCPBA/ MsCl ./ EbNCHCI, CH,CI,

3) prep TLC

(73%)

>

"3Rs"'". [

+

4

-

p

o

A

c

]

(3RS,6RS)-I90

Scheme 662

this mixture was bioactive. Then, (3S,6RS)- 190 and (3R,6RS)-190 were synthesized by the same method as shown in Scheme 663, starting from (S)- and

h

1) n-BuLi I hexane

2) +O

OAC >v

I C5HsN-ES0

3) MCPFIA 4) prep TLC

A

(3S.6R)- 190

[ale not repofled

Scheme 663

322

The Synthesis of Insect Pheromones, 1979-1989

(R)-citronellol, respectively. Only (3S,6RS)-190 was bioactive. Finally, starting from (8)-citronellol, both (3S,6R)-190and (3S,6S)-190 were synthesized (Scheme 663), and the former was shown to be more active than the latter. The natural pheromone was identical to (3S,6R)-190 by capillary GLC. The byproduct with a tetrasubstituted double bond was removed by epoxidation, followed by preparative TLC.837 (-)-Dihydrocarvone was converted to (3S,6R)-190 by Baudouy and Maliverney (Scheme 664).s38In this synthesis, the two chiral centers of the starting

’

Ac20

I)NaOH/aqEK)H

2) LiAIH,

E$O

A

(900’4

A

2) Mel,Nal/ DMF (60%)

OAC (94%)

A

(3S.6R)- 190

[a],” -Q’(CHCI,)

1) PhSMe,n-BuLi/THF

& ,

(86%)

Scheme 664

material were brought into the final product, thus eliminating the tedious separation problem in the course of the synthesis. Becker and Sahali started from (R)-limonene and prepared (3S,6R)-190(Scheme 665).839The asymmetric Michael reaction yielded the adduct with 80% d.e., which gave (3S,6R)-190of 90%purity. Dragan et al. also reported a synthesis of 190.840 Since 1979, nine new syntheses of (+)-191 or (R)-191 have been reported. Cooke and Burman prepared ( +)-191 by using an unsaturated acylphosphorane (Scheme 666).84’Avery short synthesis of (f)-191 was reported by Celebuski and Rosenblum employing an organoiron reagent (Scheme 667).842 Four out of the seven enantioselective syntheses of (R,Z)-191employed optically active monoterpenes as the starting materials. (S)-(+)-Camone was converted to (R,Z)-191 by Caine and Crews as shown in Scheme 668.843Hutch-

17. lsoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

323

ail HCI

(97%)

b

O

1) U / E$O

1) MsCl I Et,N-CH,CI,

H

CUQF,

A

2) UBr/ THF

(6p/.)

3)BF3.0Eb

i

OH

2) L&IH./ELO

(90%)-

i

AcCl ESN.E$O

OAc

(3S,6R)- 190 (3S:3R=9:1) [alono1 specified

3S:3R=9:1

Scheme 665

c 1 4 c 0 2 ~ ~NaOMe '

Ph,P=CHCO,Bu' CI +cocI

C,H,

PPh,

(91%)

OH

HO

CI

MeOH (74%)

I)DHP.HCI 2) NaBr/

>

Po

~

' O

T

H

Br

(53%)

1) K,CO, / MeOH

PPh. PPh, 1) Ao20 / CSHSN 2) Ph3P=CH2/THF' (52%)

(*b

191 (Z:E=B8:2)

Scheme 666

2) NaOH / aq E O H (pH 9-10) heal (84%)

P

(87%)

324

The Synthesis of Insect Pheromones, 1979-1989

Fp=q5-C6H5Fe(CO),

Scheme 667

[ +Tq ]

0 1) NaBH,.CeCI, MeOH

1) Ac20 / CH ,N ,

OH

2) Ac,O I CH ,N ,' OAc 3)chromatog.

(85%)

(52%)

15

1)HCONH, PdCI,(PPh,),/ dioxane

0II

'

/

cAoJ

.

4.

A 89

2) flash chromalog.

do A

11

(R,Z)-191

Scheme 668

inson and Money started from (+)-camphor, and an acyclic intermediate D was obtained after two-ring cleavage reactions (Scheme 669, A --* B and C + D).844 Their synthesis was completed at the stage of E, which had been converted to 191 previously (Scheme 193, Ref. 1 ) . By employing (R)-limonene as the starting material, Becker and Sahali synthesized a 67 : 33 mixture of (R,Z)-191and (R,E)-191 (Scheme 670).839(R)-Limonene was converted by Baudouy and Prince to (R,Z)-191 in 25% overall yield (Scheme 671).845Their synthesis afforded a final product of high purity. Especially noteworthy is the stereoselective elaboration of the (2)-trisubstituted double bond of 191. Three papers have appeared on the chemical asymmetric syntheses of

A

(t)-Canphor

I os+

1) LAM,

(68%) V

C

H

O

A

6

-

OH-'

2) PDC / CH,CI,>

A

'

I)Ph3P=CH2/THF

I

2) (n.Bu),NF l THF (71%)

(75%)

OH

(625h)

A

(1078)

E

PDC / CH,CI,

(R.Z)-lSl

Scheme 669

I ) Ph,PEtBr.NaN(SiMe,),

Sc56m !e

A

A

/ THF

CHO 2) l7, NaN(SiMe,),

A + ocJ

3) AcCl/ El,N.EbO

A

(R,Z)-lgl

(71%)

(R).Limonene

A '

A

0

OAc

(R.E)-191

(>9eQhe e )

67

:

33

(a)o no1specilied.

Scheme 670

y

A

I)03/MsOH 2)(H,N),CSlWH

3) HC(OMe),

, bkt)M;Y A

~

CeClj6H20/MeOH

(68%)

(R)-(t)-Lirnonene

NaH,PhCH2Br (n-Bu),NI / THF

(90%)

(66%)

v A

c::HzPh A

>

COCH,t'h

2) I-BuNH2/ EbO MS 4A

> -LDA / THF ESSiCI

- N Bu' Et,Si G H 2 P h

(70%)

(quW

1) s-Buti /THF

1) LiAIH, / EGO

& .,- -

:HO

3) HCiO, /aq THF (727.1

"("-

1) (COCI),,DMSO EI,N / CH2C12

2) A

3)(CO,H), 1 H$J 4) C,H,NHCI /CH,CI,

1) LDA,(E(O),POCI / THF 2) Li lliq NH,,THF

OCHzPh

2) L i l NH, (88%)

/;t;N ;)C;l

A

*OH

OH S)LiAIH,/E$O (85%)

-6'(CHCI,)

Scheme 671

325

326

The Synthesis of Insect Pheromones, 1979-1989

(R,Z)-191. In the synthesis by Leznoff et al., an aldehyde (C in Scheme 672 and B in Scheme 673) was chosen as the key intermediate.846 Mukaiyama's

(74%)

THF (88%)

Scheme 673

asymmetric Michael addition using (-)-ephedrine as the chiral auxiliary was first tried in yielding @)-aldehyde of 86% e.e. (Scheme 672).846The key-step was the Michael addition of isopropenylmagnesium bromide to A yielding B, which was hydrolyzed to C. Then Koga's method for the Michael addition by using the aldimine A was tested, giving (R)-aldehyde of > 99% e.e. (Scheme 673).846Conversion of the aldehyde to 191 was known. Oppolzer and Stevenson synthesized (R,Z)-191 by asymmetric 1,4-addition of isopropenylcopper to a chiral enoate A to give B as the key-step (Scheme 674).847Addition of isopropenylcopper to chiral a,P-unsaturated acetal A to give B was the key-step of the synthesis of aldehyde C by Mangeney et al. (Scheme 675).848A new synthesis of (*)-191 was briefly discussed by C ~ h e n . ' ~ ~

0. (S,E)-3,9-Dirnethyl-6-isopropyl-5,8-decadienyl Acetate 192

(cI 7H3002)

This is the sex pheromone of the yellow scale (Aonidiellu cirrinu). The first synthesis of (f)-192was reported by Anderson and Henrick (Scheme 676).850

327

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

(72.4%)

(R.Z)-191

[a],-7.14' (CHCIJ

Scheme 674 J+F OE'

1)

2)H20

-OEt

y

(*CULi

'

B

Ho

OH

TsOH

E l-

\ o

:

OEI

0

W

(overall 50%)

C

H

A

c

'

O

85%e.e.

-

')

'o

y % '

~cu.BF,.PEun,,

LiEr

2)H20 3) Ac20,DMPIP / C,H,N

A

A (R.2)-191

Scheme 675

&)$

Z.E.4.1

(60%)

OMEM 21)CI )A;O/C:CCO H5N H/EIOH

>Q

OAc-k

Y

(65%) 3)prep.GLC

4 (RS.E).182

Scheme 676

:

1

O

A

c

328

The Synthesis of Insect Pheromones, 1979-1989

GLC purification of the final product was followed by bioassay to prove (RS,E)-192 as b i o a c t i ~ e . ~A~synthesis ' of (RS,E)-192 and (RS,Z)-192 (Scheme 194, Ref. 1) was published in full detail."' Three enantioselective syntheses of (S,E)-192 have been reported. Mori's first synthesis began with (R)-citronellic acid and employed Still's [2.3]Wittig rearrangement as the key-step to generate the E-double bond (Scheme 677).8s2

The overall yield of this synthesis, however, was poor. The second and improved synthesis of 191 by Mori and Kuwahara (Scheme 678) was more effi-

OGH,Ph

Z)A~,O/C,H,N' 1)Li/NH3

1)KH,(n-Bu),SnCH,I 2)n-BuLVTHF (74%)

1)CrO,.2C,H6N

'

OCH,ph

HO$

2)Me2C-PPh3

(65%)

'

OCH,Ph

)+IOAC Similarly:

OHC

(77%) IR,E)-lSZ

[ u ] ,+~l l.5°(hexane)

Scheme 678

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

329

cient, and furnished (R,E)-192 and (S,E)-192 in 10% and 7 % overall yield, respectively, from methyl (R)-~itronellate.~~’ The enantiomers of 192 were tested on the yellow scale and only the S-enantiomer was shown to be bioact i ~ e In. Julia’s ~ ~ ~ synthesis of (R,E)-192 (Scheme 679), the key-step was the

-tSic1,EI,N DMAP/CH,CI, (97%)

>*oAi+

I

SO,Ph

NaOH

l)NaEH,/aqMeOH Z)Ac,O,DMAP E$N/CH2C12

I

SOzPh

(94%)

(8W

(32%)

(36%)

DMAP/CHzCI,

(96%)

chrcinatcg.(SO,-Ag NO,) OAc

A

(R.E)-192 (3lm9) (a]? -9.48’(n.hexane)

Scheme 679

introduction of the isopropyl group by the stereoselective cross-coupling reaction of the diene sulfone with isopropylmagnesium chloride in the presence of ferric chloride.855 A new synthesis of (RS,E)-192 was recently reported by Millar using silylcupration of an alkyne as the beginning step to construct the trisubstituted double bond (Scheme 680). 856

330

The Synthesis of Insect Pheromones, 1979-1989

P. (R,Z)-3,9-Dimethyl-6-isopropenyl-3,9-decadienyl Propanoate 193 (C18H3002)

This is the female-produced sex pheromone of the white peach scale (Pseuduufucaspis pentag~na).~"Starting from the enantiomers of limonene, Heath et al. synthesized all of the stereoisomers of 193 (Scheme 681) and found (R,Z)-193

to be b i o a ~ t i v e . ~They ~ ' . ~ also ~ ~ achieved the selective construction of the trisubstituted (Z)-double bond (Scheme 682).858

Scheme 682

Q. 6,10,14-Trimethyl-2-pentadecanol194 (C18H380) This is the female-produced sex pheromone of the rice moth (Corcyru cephuA synthesis of 194,which resulted in the preparation of a mixture of all of the eight possible stereoisomers, was achieved by Hall et al. (Scheme 683).8s9The synthetic stereoisomeric mixture of 194 significantly attracted the male moths at 2 ng level. The enantioselective synthesis of four out of the eight stereoisomers of 194 was carried out by Mori et al. employing (R)-citronellol, methyl (R)-or (S)-3-hydroxy-2-methylpropanoate, and ethyl (R)- or (S)-3-hy-

17. Isoprenoid Alcohols, Formate, Acetates, Propanoates, and Epoxides

331

0

(25%)

(75%)

194

Scheme 683

droxybutanoate as the chiral building blocks.860Scheme 684 illustrates the synthesis of (2R,6R, 10R)-194, which is as active as the natural pheromone.860

’

LiAIH,,CoCI,

-0,

(R)-Citronelloi

THF (85%)

H O ~i C O , M e

,PPTS

1)TsCUC H,N 2)LiQrlD;F (84%)

O -H

~

(29%5%3.e.)

E$d

THPOJC0,MB

LAlH

>

’

A

THPO-OH

puriliedas 3.5DNB (-1050/a.e.)

l)TsCUC,H,N P)NallMe,CO 3)PhSOzNa/DMF’ (71% overall yield) A

t

6

THPO-SO2Ph B

*.

THF.HMPA n-BuLi (76%)

Na.HQ ElOH W2Ph

>

U

O

T

(6956)

H

P (67%)

uO >u H P l)TsCUC,H,N 2)PhSNdMeOH

MCPBA) CHZC12

(93%)

(68%)

U

O

sh

P

C

~ C o z E 1

OTHP

OTHP 1)Na-Hg/EIOH

C.nBuLi

i THF-HMPA)

2ITsOH/MeOH

(2R.6R, lOR)-194

la], 4.4°(penma)

Scheme 684

R. (1’S,3’R,4‘S,Z)-2-(3’,4’-Epoxy-4’-methylcyclohexyl)-6methylhepta-2,s-diene 195 (C 15H240) and Its (3‘S,4’R)-Isomer 196 This is the male-produced sex pheromone of the green stink bug (Nezuru virid ~ l a ) . ~ ~The ’ * *Brazilian ~* population of N . viridula employs [runs-epoxide 195

332

The Synthesis of Insect Pheromones, 1979-1989

as its pheromone,'" while the ratio of 195 to 196 from the Japanese N . viridula was essentially 1 : 1, as compared to the 3 : 1 ratio for the U.S. N . viridula.x62 Synthesis of the eight possible stereoisomers of 195 by Baker et al. was followed by their bioassay against the Brazilian population of the stink bug to demonstrate the natural pheromone as 195.86'Baker's synthesis of 195 and 196 is shown in Scheme 685.x6'Marron and Nicolaou also prepared the enantiomers

*,'OH

8

I)MCPBIVCH2C12

T

3)sepn. as salb wilh

p-loluenesulfonic acid

A

A

1)Mel

2)KOHaq

I

(S).Limonene

A

(l'S.3'R.4'S,Z)-195

la), -I~.~'(cHCI,)

cf.(l'R,3'S,4'R,Z),l95:[al, + 19.1'(CHCI,)

Similarly:

B

%+ (l'S,3'S,4'R,Z)-198

Scheme 685

>

g' A

E-Isomer (Z:E=l:l)

4,

E-lsomer

of both 195 and 196 starting from the enantiomers of limonene oxide (Scheme 686).863 18. ISOPRENOID ALDEHYDES, KETONES, ACIDS, ESTERS, AND LACTONES AS PHEROMONES

A. Grandisal (cis-1-Isopropenyl-1-methylcyclobutaneethanal) 197 (C10H160)

This is a component of the male-produced aggregation pheromone of the northern pine weevil (Pissodes appr~ximatus),~~ Engelmann spruce weevil ( P .

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

A

I)LDA(l.leq) P)(ElO),POCI B)LDA(P.Seq) (60%)

?Qo Similarly :

7

0 i

i ; s'

-

Me

Cuti

H ;F (97%)

333

'

(l'R,3R,4S,Z)-lS6 +34.4Z0(CHzCI,)

(1'R,3'S,4'R,Z)-195 [ajDZ6 t l 9 36°(CHzCi2)

Scheme 686

srrobi),864and deodar weevil (P.n e r n ~ r e n s i s ) , 'together ~~ with grandisol (183). Grandisol (183) can be oxidized to grandisal (197), but the attempted purification of (f)-197 by silica gel chromatography resulted in severe decornposition (Scheme 687).866

Scheme 687

334

The Synthesis of Insect Pheromones, 1979-1989

B. (E)-2-Ochtoden-l-al [(E)-3,3-Dirnetyl-ALi8-cyclohexaneethanal] 198 (CIOHI60) and (Z)-2-Ochtoden-l-al 199 (CloH160) These two are the components of the male-produced sex pheromone of the boll weevil (Anrhonornus grandis). Recently, Dickens and Prestwich suggested that 199 is not essential for attraction of the boll Several new syntheses of 198 and 199 have been published since 1979. Masaki et al. prepared a 75 :25 mixture of 198 and 199 by oxidizing the corresponding alcohol mixture (187)with manganese dioxide (Scheme 654).830*83' The key-step of Mandai's synthesis of a mixture of 198 and 199 was the cyclization of sulfide A to B (Scheme 688).868Ghosh et al. synthesized a mixture

-

ci

HC02H heat (70%)

(74%)

>

Fsph l)H,OJdioxane 2)Ac,O.(CF,CO),O

>

B

A

CHO

198+lSS

Scheme 688

of 198 and 199 starting from 3,3-dimethylcyclohexanone(Scheme 689).869Ger-

,

$2H

LiCI,NaHCO, H20,DMS0 16S°C.3h

( O W

(70%)

CN

l)HBr/CH,CI, P)Et,N/C,H, heal (70%)

CHO l)(i-Bu)fiiH

(E:Z-3.3:1)

dN

,

P)NH,CIaq (80.80%)

> isatiw

Scheme 689

aniolene was the starting material for Nomura and Fujihara's synthesis of 198 and 199 (Scheme 690).870They found it possible to separate the 3,5-dinitrobenzoates of 187 and its E-isomer by recrystallization, and therefore, they were able to prepare pure 198 and 199. Mori and Itou prepared pure 198 and 199 by oxidizing (E)-187and (2)-187as shown in Scheme 655.832 A stereoselective synthesis of these aldehydes was reported by Harris and Weiler by means of a radical cyclization-elimination reaction to selectively generate exocyclic alkenes (Scheme 691).871Negishi et al. treated 7-bromo-2-io-

335

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

CH,OH

i)LiAIH,E$O Z)HdPd-C,MeOH (59%)

i)T6CVC5H5N 2)I-BuOWDMSO (68%)

o

NO2

i )LiAIH,/E$0(76%)

~

'

o mp 72.74% ' ~

N

l)MeZNCH(OEt),.heal 2)KOH/MeOH (E5%)

KOH

T

~

(32%) MeOH o z

O

H

107

CrO, Me,co (27%)

rcn

~

199

3)Recrystn from MeCN

KOH

MeOH (28%)

NO, mp 52-55OC

>

(24%)

198

Scheme 690

tk

HO-

I )OHP,TsOH/CH,Clz 2)Zn.BuLi. THF Aco.,'i'a'

-

(75%)

-wOTHP 1lUAIH.TTHF . 2)Ph,PBr~CH2CI, 3)DHP.TsOHIMeOH (55%)

THPo-c02H

'

Me02C<

l)LihCH,H,N(CH,),NH~OMSO

OTHP

(n-Bu,SnCuSPh)U

2)MeUITHF;CICOZMe (75%)

THF -40% (86%)

&

A

\ y

SnBu"g

2)(CF3S02),0/C5H5N 1)TsOHIMeOH ,CH,CI, 3)(n-Bu),NI/C,H,,heaI (76%)

C0,Me

I

(n-Bu),SnH AIBN,C,H, 85OC

(35%)

14

Me0,C

d-

+

:

1

SnBun3

A

n.Bu3SnCu*Me,S THF.-7B0C (75%)

AIBN.C,H, (n-Bu),SnH 85% (48%)

SnBun3

>

b+&+ @

B)(n.Bu),N 2)(CF,S0,),0/C5H,N.CH,CI, 1)TsOHIMeOH I/C,H,.heal

OTHP

77

l)UAIH,/Et,O Z)CrO,*C,H,N/CH,CI,

Tb

B c / 3 c

&

i

;

~

>

Ms02C$

(84%)

1

Meo2cb

i)LiAIH,/E$O

>

2)CrOJ.C,H,N/CH,CI, 189

' 198

Scheme 691

336

The Synthesis of Insect Pheromones, 1979-1989

doalkene A with n-butyllithium to effect the stereoselective cyclialkylation reaction yielding B, which was converted to (E)-alcohol C (Scheme 692).872

1) UAIH,/NaOMe:I,

C. (E,E)-Farnesal [(2E,6E)-3,7,ll-Trimethyldodeca-2,6,lO-trienal] 200 (C15H240)and Its (22,6E)-Isomer 201 A blend of 200 and 201 was isolated as a male wing-gland pheromone of the rice moth (Corcyra cephalonica), which induces the attraction of female moths.873Both 200 and 201 were prepared by oxidation of (E,E)-farnesol and its (Z,E)-isomer (Scheme 693).873(Z,E)-Famesal (201) readily isomerizes to 200.

200

100-fokl e x w s MnOz

hexane

OH

201

CHO

Scheme 693

D. (-)-Periplanone-B 202 (C1 5 H 2 0 0 3 ) This is one of the two major pheromone components produced by female American cockroaches (Periplaneta americana). Since the first synthesis of 202 by W.C. Still in 1979 (Scheme 281, Ref. 11, four syntheses of (+)-202 and two syntheses of the natural enantiomer (-)-202 have been published.

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

337

(1) Syntheses of (f)-Periplanone-B The cyclobutene-bridgehead olefin route (Scheme 694) was developed by Schreiber and S a n t i ~ ~ iIn . ' ~this ~ synthesis, cyclobutene-bridgehead olefin A was

2

n

v

(75%)

A

:

1

0

(7 Ph)

'

,,

(83%)

2)ApO,NaOAdTHF 3)KpOpqMeOH (58%)

Me,S'I'.NaWDMSO-THF

~

&O

(62%) (*).202

Scheme 694

themolyzed to cis-diene B, photoisomerization of which yielded trans-dienone C. The dienone C was further functionalized to give (f)-202.The overall yield of (+)-202by the Schreiber 13-step synthesis was 1.7%.874 Hauptmann et al. improved Still's first synthesis of 202 by the Diels-Alder synthesis (A B -+ C) of C, from which the key-intermediate D for the oxyCope rearrangement (D E F) was prepared as shown in Scheme 695.875 In this synthesis, (+)-202was obtained as crystals, and, therefore, it was possible to carry out its X-ray analysis. The overall yield of (+)-202by this route was 1 % in 16 steps. In these two syntheses, the epoxidation of the a,@-unsaturated ketone (D E in Scheme 694 and G H in Scheme 695) was not highly selective, and yielded ca. 20% of the undesired a-epoxide. Without recourse to the oxy-Cope rearrangement, Takahashi et al. constructed the 10-membered ring by the intramolecular alkylation (A B in Scheme 696).876In their synthesis, the epoxidation step (C D) was selective

+

+

+

+

-+

-+

-+

%

lp.5N.NaOWMeOH P)PCC/AI,O,,E$O (54%)

THPO~

THPOi

6

2)Me3SiCI 1)KWHF,

THPO

1) LiBH(s-Bu),

t.BuPh,SiCI

2) LAIH,

(50%)

(75%)

I

J.

Ho

(syn :anti = 9 : 1)

foH Ph

UN(SiMe,),

mp. 109-fflOc

Scheme 696

338

H, I Lindlar.Pd ( 9 W

2) H'

(78%)

EbN , OMAP (76%)

(f).202

>

18. lsoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

339

to give only the desired 0-epoxide. The overall yield of (f)-202by the Takahashi 23-step synthesis was 0.5%. Cauwberghs and De Clercq developed a formal synthesis of (f)-202via trienone F, which had been employed by Schreiber as the key-intermediate (Scheme 697).877Addition of dilithiated allene to A gave B, which was heated 1) 2eq LDA/ THF

1) leq n-BuLiITHF

C6H6s800C

2) 5eq uc.c=cLi

(65% fromA))

H

(60%)

~

H

B

A

C

5 C

4

i D mesirylene, 7 164OC. 24h C:D-2:1 0

1) 2eq n.BuLi I

2) (CF,SO,),O,

€60 -20%

1

-

THF , - S 0 C (29%)

Scheme 697

to effect the intramolecular Diels-Alder reaction to give two exo-adducts, C and D. Subsequently, C was first reduced and then reductively cleaved to furnish E. The Grob fragmentation of E gave (+)-F in 4.2% overall yield. Schreiber and Santini converted (2)-F to (f)-202in 24.8% yield.874Therefore, the formal overall yield of (f)-202by the De Clercq synthesis was 1 %.

(2) Syntheses of (-)-Periplanone-B Two different enantioselective syntheses of (-)-periplanone-B (202 = naturally occurring enantiomer) were reported by Mori's group. In the first synthesis, (R)-(+)-limonene was chosen as the starting material, and the 10-membered ring was constructed by the intramolecular alkylation (A --t B) as shown in Scheme 698.878*879 B was then converted to ketone C, the (-)-enantiomer of the Schreiber intermediate, which finally furnished crystalline (-)-202in 0.5 % overall yield via 29 steps from (R)-(+)-limonene. In the second enantioselective synthesis, (-)-periplanone-B (202)was synthesized from (S)-(-)-3-cyclohexene- l-carboxylic acid (A) through 18 steps in 1 1 % overall yield (Scheme 699).880*88' The key-step was the oxy-Cope rear-

. . (R)-(+).Limonene

/ElpH20

1) OsO,-NaIO, 2) LNH./EL,O

- -

3) Ac20 / C5H5N (76%)

’

& &

Me0,C

SPh

4) MEMCi , I-Pr,NEI/ CH,CI,

I ) 75% AcOH aq , heal 2) PhSCH,CO@, LDAl THF 3) AcpNaOAc 4)NaOMe/MaOH 5) TSCl/ C5H5N (68%) 1) UAIH, / E 4 0

2) PhCOCl /C5H5N.THF , DMAP

3)Me,SiCI , Nal / MeCN (88%) PhCOO

&

’ Na,

C

(62%)

NaN(SiMeJ2

an &

DME,heal (57%)

THF

-7OoC, 6min (86%)

B

1) UN(SiMe,), /THF

MEMO

TsO

’

(a%)

1) ‘JN(Qm2)3

, PhSSO,Ph

Mo05*HMPA*C5H,N 1.BuOOH

2) NaiO, / aq Me0 3) CaCO,, BHTlIolume

KH/THF (25% from C)

> (75%)

1) Me,SI, n&Li / THF 2) (n.Bu),NFITHF CH,CI, (-).202 mp.57.0-57.5°C [a],,P653’ (hexme)

(7044

Scheme 698

9

1) UAIH, / EbO 2) MnO, / CHCI,

KI, , NaHCO, aq

>

CH,CI,

CO,H

3)

7,Yg ’ $q/ aNoz 0

(W-A LDA/ THF

EEO

B

MsCl , EI,N

A ,$CHO

CH,CI,

EEO

SePh

OH

(51% from B)

EEO

(86%)

3,

-

EEO

D

I

SeCN

1) Me,SI , n-BuLi / THF

6

2) LiN(SiMe,),/

THF MoO,.HMPAC,H,N

3) I-BuMe,SiCI, imidarole DMF (77%)

Se

(n-Bu)$P/ THF (73%)

EEO 1) H202/ THF

1) KH , I.BuOOH/THF 2) PPTS / EtOH

(74%)

O

PPTS/CHZCIz (86% from A)

PDC DMF (92%)

(73%)

(.)-202

Scheme 699 340

mp. 55.5-57.5% [a):’ -552’ (hexane)

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

341

rangement of C to give D. This efficient synthesis of (-)-202 allowed the preparation of a substantial quantity of the crystalline pheromone.

E. (-)-Periplanone-A 203 (CI5HZ0O2) This name was first given to a compound isolated by Persoons et al. for the pheromone component produced by female American cockroaches (Periplaneta urnericuna). They proposed structure A for it (Scheme 700), and demonstrated its facile rearrangement to a stable and biologically inactive compound B.882.883

A 0

203

C

0

h II

0

OH

NaBH, I MaOH (80%)

R1

E ( X-ray analysis )

Scheme 700

The structure B was supported by a synthesis of its racemate from C and 1,3butadiene by Mori and I g a r a ~ h i . " The ~ true structure of Persoons's compound was shown to be not A but D, which was the thermal decomposition product of the genuine pheromone 203.885*'229 An X-ray analysis of E was the key in solving the problem.885 The compound isolated by Persoons turned out to be biologically inactive, and, therefore, D was given the name isoperiplanoneA.886A concise review on this structural problem was described by Mori et a1.887 In 1986, Hauptmann et al. isolated 203 from the American cockroach, named it periplanone-A, synthesized (*)-203, and found it to be bioactive.888 Their synthesis started from the trienone A (Scheme 701),888which had served as an intermediate in Still's first synthesis of p e r i p 1 a n 0 n e - B . ~ ' ~ ' ~ ~ ~ Two other syntheses of (*)-203have been reported. Shizuri et al. converted germacrene-D to tetraenone A, and epoxidized A as shown in Scheme 702.890 In Shizuri's case, (f)-203 and its epimer were obtained in a ratio of 1.7 : 1.O, while Hauptmann et al. reported a ratio of 99 : 1. Another synthesis of (f)-203 was achieved by Takahashi et al. (Scheme 703).89' In Takahashi's periplanoneB synthesis,876diol B was used as the intermediate. Its anri-isomer A was also

I-&COH

-2O0C (67%)

99

1

(fp203

Scheme 701

GermscreneD

(fp203(53%)

A

Macdonalds

epoxy ketone (31%)

Scheme 702

I)Cp,liCH,CIAIMe, 2) PPTS I MeOH 3) Cr03C,HSN

D

13 (?)-203

Scheme 703

342

I0 Madonalds

epoxy kelOnE

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

343

obtained as the minor product. This isomer A was convened to ketone C in the same manner as in the case of the synthesis of (f)-periplanone-B. The ketone C was further manipulated to give tetraenone D, the intermediate common to others.888q890 Epoxidation of D yielded a 1 . 3 : 1.0 mixture of (f)-203and its epimer, which is in accord with Shizuri's result.890The epimer of (f)-203was first synthesized by Macdonald et al., starting from Still's intermediate (Scheme 704).892The epimer, which was called Macdonald's epoxy ketone, was biologically inactive.

EEO

I

?Sit

(73%)

Macdonalds epoxy ketone

Scheme 704

Kuwahara and Mori achieved an enantioselective synthesis of both the enantiomers of periplanone-A (203) and proved only (-)-203 to be bioactive.887. 1229 Their synthesis (Scheme 705) furnished both the enantiomers of 203 as crystals. Nishino et al. showed that periplanone-A[( 9-2031 and periplanoneB[( -)-2021 participate specifically with the corresponding sex pheromone receptors. 893

F. Periplanone-C 204 (CI5H2,,0)and Periplanone-D 205 (C 15H220) These two compounds are minor and less bioactive components of the femaleproduced sex pheromone of the American cockroach (Periplanefa americana). These were originally called penplanone-D I and periplanone-D2, respect i ~ e l y but , ~ were ~ ~ later given their present names.886 (f)-Periplanone-C (204)was an intermediate of Hauptmann's synthesis of (f)-periplanone-A (203,(Scheme 701).888Reduction of (f)-204yielded (*)penplanone-D (205, Scheme 706).894

344

The Synthesis of Insect Pheromones, 1979-1989

(60%)

EEO' D(17%)

C(43%)

LiN(SIMe,),

SeCN lTHF (59%)

EEO/

(67%)

(86%)

E

(-)-203

mp 42-44OC [a]," -574' (hexane)

(+)-203 mp. 42-44OC

la1025tS4' (hexane)

Scheme 705

(33.204

(%]-205

Scheme 706

Macdonald's epoxy ketone

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

345

G. Callosobruchusic Acid [(E)-3,7-Dimethyl-2-octene-l,B-dioic Acid] 206 (ClOH1604) In 1981 Yamamoto and his co-workers isolated and identified the copulation release pheromone of the azuki bean weevil (Cullosobruchus chinensis), which induces the male to extrude his genital organ and attempt copulation.895 They named it erectin and found it to consist of two synergistically acting fractions. One was a mixture of methyl-branched hydrocarbons such as 11,15-dimethyltritriacontane. The other was callosobruchusic acid (206).895 Two syntheses of (*)-206 have been reported. Tanaka et al. converted gerany1 acetate into (f)-206 as shown in Scheme 707.896Kang and Lee synthesized (f)-206 starting from 2,6-dimethylcyclohexanone(Scheme 708).897

OHC

UOAC + , H

O

~

o

ND2

aqNaOH

A

Jonescro3 c

>

H02C-0Ac

HO,C U

C

O

,

"

(fI.2M mp. 78-81'C

Scheme 707

(MeO)2POCHzCOzMe NaH / DME

(so%)

>

MeOZC eM2O C,&, ( ,

d'lHCi heat (85%)

,

HO2C

(+)-2W

Scheme 708

Mori et al. prepared both the enantiomers of 206 by employing the asymmetric alkylation procedure developed by Evans (Scheme 709).898Starting from methyl 6,7-epoxygeranate (A), iodide B was synthesized, and it was used for the asymmetric alkylation of prolinol propanamide. Although (S)-206 was about twice as active as (R)-206, both the enantiomers were b i o a ~ t i v e Gramatica .~~~

The Synthesis of Insect Pheromones, 1979-1989

346

u

C

O

,

M

e

= .>

w

>

aqEOH (53% from A)

O

,

M

y;;:

e

(73%)

A

Methyl geranale

NaBH,

C

HO&C02p&

I &CO,Me

TsC1'C5H5N,

2) Nal/ M,CO (75%)

(43%)

E

, .

OHC'dbco2Mo

dJy* 3eq LDA THF-HMPA

(51-206 mp. ~1.91' C

lalD2'+10.5' (CHCI,) (92% e.e.)

(R).206 rnp. 91.92'~ [alon -I 1.7' (CHCI,) (93% e.e.1

Scheme 709

et al. prepared (S)-206by means of asymmetric reduction with baker's yeast (Scheme 7 10).835

Scheme 710

H. (2E,6E)-lO-Hydroxy-3,7-dimethyl-2,6-decadienoic Acid 207 (C12H2003)

This is the major component in the hairpencil secretion of the male monarch butterfly (Danaus plexippus). Sum and Weiler published a full paper of their synthesis of 207 (Scheme 71 l).899

18. lsoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

347

(71%)

(99%)

(92%)

(91%)

207

Scheme 711

I. (2E,6E)-3,7-Dirnethyl-2,6-decadiene-l,lO-dioic Acid 208 (C12H1802) This is also a component in the hairpencil secretion of the male monarch butterfly (Dunuus plexippus). Trost et al. developed a synthesis of the dimethyl ester of 208, starting from methallyl phenyl sulfone by means of palladiumcatalyzed carbon-carbon bond formation (Scheme 7 12).900Another synthesis of

(61%)

NaCH(CO,Me), Pd[Ph,P(CH,),PPh,k THF (l?a%)

MeO,C

UCO,M > L'''3Hz0

NaCN I DMF 12O0C (58%)

MeO,C

Dimethyl ester 01 208

Scheme 712

the dimethyl ester of 208 by Tsuji et al. also resulted from the application of organopalladium chemistry as shown in Scheme 713."' It should be noted that the reaction of A with methyl acetoacetate in the presence of the palladium catalyst yielded pure (E)-B.

348

The Synthesis of Insect Pheromones, 1979-1989 0

/LL C o p e 1) NaOH / aq MeOH

2)H' 3) AczO / C,H,N

(7094)

>

(62%)

0

),,C02Me

5md% Pd(PPh3J,

NaOMe

NaH / THF (91%)

(EZ).A

Meo2c

F1.B

0

MeOH (81%)

II

MeO,C

do

(MeO),PCHZCO,Me NaH / DMF

M e20C,&,&, MeO,C Dimehyl ester of 208

Scheme 713

J. Eldanolide [(3S,4R)-3,7-Dimethyl-6-octen-4-olide] 209 (C

602)

This is the male-produced sex attractant pheromone isolated from the wing glands of the African sugarcane borer (Eldana saccharina).902q903

(1) Syntheses of (+)-Eldanolide Ten different syntheses of (rt)-209 have been reported. Kunesch et al. synthesized (f)-209 and confirmed their structural proposal by a route involving organocopper chemistry (Scheme 714).902,903 Chakraborty and Chandrasekaran -OH

+

hWOMe),

EtC02H heat, 140-145° (65%)

'

MCPBA I CH,CI,

(f)-ZOS

Scheme 714

prepared (+)-209 as shown in Scheme 715.904The key-step there was the oxidation of diol C to lactone D. Iriye et al. converted citral to (*)-209 and its

349

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones 1) PhCH,CI / NaH

2) BH ,,

HO?

MgBr

P h C H 2 0 T o H

/ H202, &OH

THPOJ

A H, / Pd.CsCO,

PhCHz,"ty-7

quinoline , TsOH I W H (72% horn A)

C

P , hCHz%

OH

Ag,CO,celite

reflux CH ,, (75%)

OH HO

0 D

HO*~

H,IPd.C

0

(70%)

PhC

(80% from B)

B

0 (*).I09

Scheme 715

cis isomer (Scheme 7 16).905*906 Dziadulewicz and Gallagher employed y-addition of 4-methyl-3-pentanal to ketene dithioacetal A to give B as the key-step

I

I

>-.

I

NaOAc

W

C

Me2C0.HMPA

H

O

I

>-

OAC

(46%)

MnO,. NaCN

~

MeOH (75%)

c OH

1)NeBH. NiCldMBOH (57%)

0

2) prep TLC

(f)209(67%)

(4G%)

Scheme 716

in their synthesis of (&)-209(Scheme 717).907*908 Another synthesis via ketene dithioacetal was published by Fang and Hong (Scheme 7 18).909 B~

Z)DBU/CH,Cl,

(83%)

SPh

>

1) PhSH, BF,-E$O CH,CI, PhS-SPh

>

A

DBUlCH CI

(45%hai)

SPh

CHO

1) CF,CO,H/CH,CI,

wo

PhS

-78%

>

MepuLi

C

Scheme 717

(60%)

SPh

2)NaHCOdaq MeOH'

B

'

(f)-209

o

350

The Synthesis of Insect Pheromones, 1979-1989

Acid-catalyzed rearrangement of 4,5-dihydro-l,3-dioxepinA to 2,3-substituted tetrahydrofuran B was the key-step in the synthesis of ( f )-209 by Frauenrath and Philipps (Scheme 719).9’0 This synthesis is suitable for a large-scale

’

TsOH C6H12

(95%)

BF,-E$O

HC(OMe), (84%)

CrO,(OAc), ‘EHE

(47%)

’

RuCI,(PPh,),

-

NaBH,-MeOH (92%)

1) HCI-aqTHF

C

’

H

Z)N,H,.KOH

HO

TsOH O

M

O

C,H,. heal

(70%)

0

A

>

HO

4

>

(UU%)

(f)-209

Scheme 719

preparation, and 26.8 g of (f)-209was obtained. Jefford’s synthesis provided (f)-209 in only two steps from a commercially available starting material by prenylation of a silyl 1,3-dienol ether (Scheme 720).9” Barua and Schmidt used

(95%)

Scheme 720

(3-phenylthioacrylic acid and methyl propiolate as the C3 building block for the synthesis of (_+)-209(Scheme 721).9’2 Yoda et al. synthesized a mixture of (f)-209and its cis isomer as shown in Scheme 722.9’3

(2) Syntheses of Optically Active Eldanolide The natural (3S,4R)-209 was first synthesized by Mori et al. in 1982 as an intermediate in the synthesis of a marine diterpenoid aplidia~phingosine.”~ The

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

oo

Me&l E120

&OH

‘

b H OAo

HClO A

c

e

dioxad heal

o

(81%)

LiCi CC0,Me

&CHO OAc

THF

(9%)

(80%)

PhS I-BuLflHF

0

>

heal

Z)bCO,/MeOH

OH

(78%)

’

PCC CHZC12 (68%)

1) Ac.pC,H,N.

>

OAc

>

2

Raney Ni THF

A

(76%)

*

>

(90%)

?“,u” (82%) 12

O

’ +”

C02Me

OH

I ) H&ndlar C,H,N-MeOH Pd

>

(+).209

A

2) TsOH/C,H,

A d

351

(73%)

Scheme 721

(n-Bu)pH AlBNfToluene heal (72%)

>

MgMeOH (61%)

>

Mo

+ cis isomer

(+).209

(3

:

1 )

Scheme 722

details of the synthesis, together with preparation of (3R,4S)-209, were published in 1983.915As shown in Scheme 723, the synthesis led to the pure enantiomers of 209 starting from pure (R)-citronellic acid (A). The key-step was the iodolactonization of B to give C.”’ In late 1982 Vigneron et al. also reported the synthesis of both the enantiomers of 209 (Scheme 724).903.916 They prepared the enantiomers from glutamic acid, or by optical resolution or asymmetric reduction. Like Mori’s synthesis, they also employed an epoxy ester as the key-intermediate. By comparison of the CD spectrum of the natural 209 with the synthetic enantiomers, the absolute configuration of the natural eldanolide was shown to be 3S,4R. The natural enantiomer was biologically more active than its antipode by EAG testago3 Four other syntheses of optically active 209 started from natural products. Yokoyama et al. employed (-)-P-pinene (A) as the starting material and pre-

’

U

C

0

2

H

a

'

IdMeCN -2ooc

(76%)

,do \a$$

(3R,4S)-C

>o+cozh+3

'))+,MgBr

.CuBr

THF

(77%)

(89%)

2) Prep GLC

>

-0

(3R,4S)-20S (CHCI,)

1 a 1 ~ ~ - 5 5(EIOH) .9~

Scheme 723

0 PhCH20&%

\\

CO,H

1) 6)a-Phenethylamine (resolution) 2) HCI

OH

>

PhCHpo<\

3) NaOH aq (46% lrom (+)-alcahol)

Scheme 724

352

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

1) LiNPiflHF 2) PhSSPh 3)MCPBA 4) heaVCCI,

353

' (20% hm 0 )

(3R.4Sk209

Scheme 725

pared the antipode of the natural 209 (Scheme 725).'" Suzuki et al. synthesized the enantiomers of 209 from ethyl lactate, using their asymmetric pinacol-type rearrangement (Scheme 726).9'8Font and his co-workers converted D-ribono-

Similarly

Scheme 726

The Synthesis of Insect Pheromones, 1979-1989

354

lactone into (3S,4R)-209 (Scheme 727).9'9.920 Starting from (S)-serine, Larchev&que et al. synthesized (3S,4R)-209 (Scheme 728).92' The key-step was the conjugate addition of methyllithium to A to give B.

""'rs-

1) Me2C0.H'

OH

Hod

NaOMe THF (85%)

mo o.Ribonolaclone

CF,C02H-Hz0

oeXo

&CO,Me

MeOH

2)TsCVC,H6N

(quanl.)

,

(

EtzO

,

(67%)

HC(OEI), THF

Y OEt

(qUW

.

.

( ~ ] ~ ~ + 5(MeOH) 0 . 7~

Scheme 727

HOYCoPH

pCO,Et

> &CO,EI

(/b2cuL'

4

NH,

E$OzO.b00C

(S)-Senne

OH

(90%)

1)

H202,

0

,

B

(55%)

(90%)

160'C

2) 40% HFlMeCN 3) TsOH/C6H6heat

Ph

imidazole 2) (i.Bu)$lH

(3%4R)-209

[alDm+53.io (MeOH)

Scheme 728

Four asymmetric syntheses of 209 have been recorded. Whittaker reported an application of Mukaiyama's asymmetric Michael addition to the synthesis of (R)-B (Scheme 729),922which was used by Mori et al. for the synthesis of (3R,4S)-209.'I5The optical yield of the asymmetric reaction, however, was not

>

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

355

Scheme 729

as high (59% e.e.). Matteson's highly successful asymmetric synthesis of (3S,4R)-209,the antipode of the natural pheromone, was achieved via pinanediol boronic esters (Scheme 730).302Biochemical reduction of a bicyclic ketone

- L A , , ,

Et,O-THF

,

(84%)

m.p. 13-16OC 88-98.5% pure

Scheme 730

(*)-A with a fungus (Mortierella remanniana) was the first step of Roberts's synthesis of (3S,4R)-209 (Scheme 731).923,924 The synthesis, however, ended

Scheme 731

356

The Synthesis of lnsect Pheromones, 1979-1989

up at the stage of lactone D. Yadav and Gadgil synthesized (3S,4R)-209 starting from an optically active allylic alcohol A, which was prepared by Sharpless kinetic resolution (Scheme 732).925 The key-step was the radical-induced cy-

Scheme 732

clization of bromoacetal B to give C. Bloch and Seck reported a synthesis of A, the immediate precursor of (3S,4R)-209(Scheme 733).926

K. (R)-Dihydroactinidiolide (2-0~0-4,4,7a-trimethyl-2,4,5,6,7,7ahexahydrobenzofuran) 210 (C, ,HI6O2) This is a component of the Queen recognition pheromone of the red imported fire ant (Solenopsis invicta), together with two other lactones (154and 155).6’I (S)-( +)-Dihydroactinidiolide (210) was first isolated from the essential oil of a Japanese plant “matatabi” (Actinidia polygama) as an attractant against Felidae animals such as cats and lions.927Sakan et al. carried out the first synthesis of (+)-210as shown in Scheme 734.927 Since then, numerous syntheses of (+)-210

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

357

have been reported (see Refs. 10-22 of Ref. 1053). For example, Chakraborty and Chandrasekaran prepared (_+)-210as shown in Scheme 735.928

Scheme 735

The absolute configuration of ( -)-dihydroactinidiolide (210) was determined as R by its derivation from zeaxanthin (Scheme 736).929Eugster and his OH 02

hv

HO

>

HO

Zeaxanthin

Scheme 736

co-workers also showed (-)-210 to be R by converting azafrin methyl ester to (-)-210 (Scheme 737).930

(-WO

(only 2.7mg)

CD (EIOH) 215nrn(-14.43)

Scheme 737

358

The Synthesis o f Insect Pheromones, 1979-1989

Four syntheses of (R)-210 have been achieved since then. First, Kienzle et al. synthesized (R)-210 (Scheme 738),93'employing baker's yeast for the asymmetric reduction of A to B.932Sato's synthesis (Scheme 739) was accomplished

(R)-210

rnp 69-71OC

Scheme 738

lul,".l

19.9°(CHC13)

(R)-210

mp 6869OC la1DL119.70 (CHCI,)

Scheme 739

by means of asymmetric synthesis of 2-hydroxy-2-methylcyclohexanone(A) using (S)-prolinol methyl ether as the chirai auxiliary.933 Mori and Nakazono synthesized both (R)-210 and (S)-210 starting from ($)-3-hydroxy-2,2-dimethylcyclohexanone (A) (Scheme 740).934The enantiomers of 210 prepared

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

THPO

MeC(OEt), EIC0,H. heat (96%)

(66%)

CO,EI

>

359

1) KOH 2) aq NaHCO,. l,-Kl/E$O 3)TsOH/MeOH

>

rnp 6768'C

[al,n+120.Qo (CHCI,)

(30%)

(R).210

mp 7O-7l0C lalDz"-121.00 (CHCI,)

Scheme 740

by this route were bioassayed by Tumlinson to reveal (R)-(-)-210 as active.622 Battiste and his co-workers prepared (R)-210 by resolving a racemic methylene lactone A (Scheme 741).935 The resolved (R,R)-Ayielded (R)-210 via tetrahydroactinidiolide B.

Ph,P=CH,

NaCH(C0,Et) ElOH

(91%)

(90%)

(70%)

'

1) NaOH aq 2)H,O' (97%) 2) SiO, chromatog. sepn

(z4p/4

L

'

LiBdDMF heal

'>

&

CO,H

"'OH

(--4c%)

0

ca 95%

(R.R).A

(96%)

(93%)

B

(50%)

(R)-210

l ~ l ~11~ (hexane) - i

Scheme 741

The Synthesis of Insect Pheromones, 1979-1989

360

L. Anastrephin (2-0~0-4-ethenyI-4,7a-dimethyl-2,4,5,6,7,7ahexahydrobenzofuran) 211 (CI2Hl8O2)and Epianastrephin 212

(c12HIS02)

These are major components of the male-produced sex pheromone of both Caribbean (Anastrepha suspensa) and Mexican (Anastrepha ludens) fruit flies.936v937 The natural products isolated from A. suspensa were mixtures of two enantiomers [(-)-isomers : (+)-isomers = 55 f 3 : 45 3].936To confirm their structural proposal, Battiste and his co-workers synthesized ( f )-211 and (*)-212 (Scheme 742)936by employing their spirooxirane route to trans-fused

+

2

:

3

R- CH-CH,. R-Me

removed

R-Me. Raney Ni DMSO

PhS

R'=CH=CH,

' (f).lll

minw product (13%)

(f)-212 (72%)

major product

(B%)

Scheme 742

y - l a c t o n e ~ . ~Far ' ~ more efficient synthesis of a 1 : 1 mixture of (+)-211and (*)-212 was reported by Saito et al., based on the cationic cyclization of (3E,SE)- 10-hydroxy-4,8-dimethyl-3,8-decadienoic acid (Scheme 743).939 Two syntheses of the enantiomers of 211 and 212 have been published, both by means of the optical resolution of the racemates. Battiste and his co-workers used (R)-( -)-phenylglycinol as the resolving agent and separated the diastereomeric amides by silica gel chromatography (Scheme 744).9'5 The amides were converted to the enantiomers of the lactones, 211 and 212. Mori and Nak-

361

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

I ) BF,*OEYCH,CIz (67%) 2) SO, chromatog.

HOC -O H ,

0

> (*).Zll

(+).212

1

1

Scheme 743

1

(40-42%) r w

b

o

(*I-211

P

') h

OH

O O H toluene. heal 2) SlO, chromatog

N

H

j

0, N

H "Ph 1NNaOH)

GI

heal (97.98%)

'"OH HO less polar mp l69-17O0C

(+)-acid(?) mp 1 0 8 - 1 0 9 ~ ~ (a1,25+23.1'(EtOH)

L=&y

~

(3aR,4S,7aR).(r).Zll mp 94-95%. [~]fl+48,8~(hexane)

= e H C O 2 H

: OH HO

more polar amorphous

mp (.).acid(7) ~OB-IW~C

(3aS,4R,7aS)+).211

[~1?-23.1 o(EOH)

+=@cozH

r.;-=@Ny:h

"'OH HO

"'OH

less polar mp 155.5-156°C

2) SiO, chromatog.

(+)-acid(?) m 9596'~ [~]:~35:4~(EtOH)

(3aR,4R,7aR).(+)412 mp 48-50°C. [a],25+74.70(hexane)

WNHI H

Ph-

OH HO more polar amorphous

(-).add(? mp 95.96 C [al:5.35.50(EIOH)

Scheme 744

(3aS,4S,7aS)-(-)-212

362

The Synthesis of Insect Pheromones, 1979-1989

more polar

(3aS,4R,7aS).(-)-211 rnp QI.O.91.SoC. [alga'-50.4°(n-hexsne)

amorphous

less polar mp en 0.81 0%

(-)-aad mp94 0-95.OOC (a]~5.41.10(EIOH)

(3aR,4R,7aR)-(t).2l2 mp 48.5.50 O'C, [a]~'5+E7.90(n.he~8n8)

Scheme 745

azono employed ( S ) - ( +)-prolinol as the resolving agent (Scheme 745).940 Mori et al. observed the formation of (+)-211and (+)-212from the corresponding (-)-acids, while Battiste et al. reported the formation of (+)-211and (+)-212 from (+)-acids. Robacker found that only treatments containing at least (Z)-3-nonen- 1-01 and/ or (3Z,62)-3,6-nonadien- 1-01 in combination with (3aS,4$,7aS)-epianastrephin (212)elicited strong behavioral responses of virgin female Mexican fruit flies (A. l ~ d e n s ) . ~ ~ ' . ~ ~ ~

M. Suspensolide [(3E78E)-4,8-DimethyI-378-decadien-10-olideJ 213 (C12HI 802) The Caribbean fruit fly (Anastrepha suspensa) is a pest of citrus, guava, and other fruits in Central and North America. The male pheromone consists of (Z)3-nonen-1-01, (32,6Z)-3,6-nonadien-l-ol, suspensolide 213, anastrephin 211, and epianastrephin 212.943

363

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

Battiste et al. synthesized 213 without any stereocontrol (Scheme 746).944A stereocontroled synthesis of 213 by Mori and Nakazono, however, was lengthy and inefficient (Scheme 747),940with the yield of the final lactonization reaction particularly requiring improvement.

&'[ +

(60%)

OH

(55%)

2)Ac O/C H N 3)H ~ L C &dn

3

&OAc]

:

2

1) Ph,P-CHCH,CO,'

2) CH,N, 3) HPLC sepn 1

1

Scheme 746

(42% trorn A )

.

(95%)

.

1)n.EuCi/HMPA-EbO

TsCl

2) bBr (quant )

E

r

'

u OTHP

DMF

B

(58%)

(67% from 6)

3) dl. HCI

Me0,C

'

1) KOH/MeOH

OH

2) dil. HCI

3) EQ,CN=NCOzEI Ph,P/C,H, (9%)

Scheme 147

>

$Lo 213

364

The Synthesis of Insect Pheromones, 1979-1989

N. (4aS,7S,7aR)-Nepetalactone214 (CIOH,402) and (lR,4aS,7S,7aR)Nepetalactol215 (CIOHI6O2)

The sex pheromone of the vetch aphid (Megoura viciae) is a synergistic mixture of nepetalactone (214) and nepetalactol (215).945*946 Nepetalactol (215) also works as the sex pheromone of the green bug (Schizaphis gr~rninurn).~~' (4aS,7S,7aR)-( +)-Nepetalactone (214) was first isolated from catnip (catmint, Nepeta cataria) in 1941 as a unique monoterpene highly attractive against cats.948The existing syntheses of nepetalactone and its relatives were reviewed by Thomas.949Therefore, only the recent syntheses, those that appeared after the isolation of 214 as the aphid pheromone, will be reviewed here. Dawson et al. reduced 214 (isolated from N. cataria) with diisobutylaluminum hydride to give 215,945whose stereochemistry was determined by the X-ray diffraction study of the crystalline 3,5-dinitrobenzoate of 215 (Scheme 748).946According to the method developed by Schreiber et Sakurai et

"I

HI

(-).215

(+).214

[a],,2"4O0 (€OH)

.

-

Scheme 748

al. synthesized the enantiomers of 214 and 215, starting from the enantiomers of citronella1 (Scheme 749).951Interestingly, to the aphid only the natural enantiomer is active,946but to cats both the enantiomers of 215 are powerful attractant~.~~'

0. Ferrulactone I [(4E,8E)-4,8-DirnethyI-4,8-decadien-lO-olide] 216

(cl Z H

18O2)

This is a macrolide aggregation pheromone produced by the male rusty grain beetle (CTyptolesteSferrugineus)and was isolated from their frass together with fermlactone I1 (161).694Geraniol was converted to 216 by Oehlschlager et al. as shown in Scheme 750.695The yield at the final step was estimated by GLC analysis of the reaction mixture, and 216 could not be isolated. They then developed a better route (Scheme 75 I ) , employing Corey's macrolactonization method for the cyclization of A to yield ca. 100 ng of 216.695Sakai and Mori

365

18. Isoprenoid Aldehydes, Ketones, Acids, Esters, and Lactones as Pheromones

(-)-214 [ul0~-21.oO(E$O)

(+)-215 [ ~ ] ~ ~ + 4(EGO) 3 . 6 ~

Scheme 749

uoH PhSCH,COCI

1) SeO&,H5N-E10H

NaHlHMPA

& & ,o

CBr,. Ph,P

0 2)NaBH,CN ~ p h 3) chromalog.

C5HY (99%)

geraniol

(quanl.)

" SPh

(46%)

b0

Raney Ni

(-45"hbyGLC)

SPh

216 (No1 isolated)

Scheme 750

LiCH2


I) Me1 2) NaOH

(37%)

geranioi

0

Br

2)NeClJDhrSO' l€Q°C. 7h (58%)

i-Pr A (73%)

Scheme 751

@C02H

1-Eu

l-BU

1) NaHlDMF

~

3) Dowex SOW (44%)

i.Pr

toluene Ph P d8-106C; h e n heal

(37%)

216

366

The Synthesis of Insect Pheromones, 1979-1989

developed another synthesis of 216, starting from (2E,6E)-famesol (Scheme 752).696The overall yield of 216 from famesol was 10.4% in seven steps. A \

O H-

1) Ac,O/C,H,N 2) N W a q DME

\

3) K&O@eOH 4) Ac20/C,H,N

Farnesol

’

(45%)

HI0,.2H20 THF-eUwr (€% 5%)I

1) Jones CrO, k,CO

>

tNtS .,q

I.Bu

‘

HO,C

2) KOH (aq) (68%)

I-Bu

&-+

i-Pr

i.Pr

OH

>

Ph3P/loluQne

216

(33%)

Scheme 752

short synthesis of 216 was published by Inanaga et al. employing intramolecular Reformatsky reaction as the key-step (Scheme 753).952 Use of samarium(I1) 0

(38%)

(47%)

Sml, WOPh

THF-HMPA I-BuCO,H

’

(78%)

Scheme 753

216

iodide was the special feature of their synthesis. Cheskis et al. prepared 216 beginning with geraniol (Scheme 754).953

(99%) MeC(OEt), OH

EICO,H.hea!’ (95%)

uc2‘E

‘

‘

OTHP

1) TsOHG5H,N/E10H

2) KOH/MsOH

(93%)

(42%)

Scheme 754

216

19. Oxygen Heterocycles as Pheromones

367

19. OXYGEN HETEROCYCLES (EXCLUDING EPOXIDES, LACTONES, HEMIACETALS, AND ACETALS) AS PHEROMONES A. Hepialone [(R)-2-Ethyl-6-methyl-2,3-dihydro-4H-pyran-4-one] 217 (C8H1202)

This is a sex-pheromonal component produced by the male moth (Hepiulus culifornicus).Kubo et al. isolated 217 from the sex scales or hairpencils of the males. The CD spectrum of 217 suggested its R-config~ration.~'~ Uchino et al. synthesized both (f)-217 and (R)-217as shown in Scheme 755.955The known (R)-ethyloxirane, which was prepared from (+)-malic acid, 1) NaWlHF 2) mBuU

3)ElCHO

>

TsOH

0

> 0

(31% overall)

(f)-217

1) HgCI, CaCOJaqMeCN

1) n-BuLimF.HMPA

2) TsOH/C6H6 (46%)

, 0 (R)-217

(51%)

[a],"+106.4°(

EIOH)

Scheme 755

was the chiral building block in Uchino's synthesis. Hayashi and Mori achieved another synthesis of (R)-217,starting from methyl (R)-3-hydroxypentanoate (Scheme 756).'56 Enantiomerically pure (R)-217was obtained through this route 0

OH &C02Me

1)DHP.TsOH 2)KOH-MeOH-H,O O)AcOH(pH 4.5)

(WX)

-lOO%e.e.

OTHPO

0

4.AA

2:; (O°C) (69%)

'

l ) N c ~ - e . ~/DMF z

Z C O 2 H

9 (R)-217

[alon +23S0(EfOH)

Scheme 756

o'MBo 2,

3)SiO2.chrornalog (1 7%)

>

368

The Synthesis of Insect Pheromones, 1979-1989

by carefully avoiding the racemization at the final stage of c y c l i z a t i ~ nYadav .~~~ and Rao reported a synthesis of (*)-217 by employing a 1,3-dipolar cycloaddition as a key step (Scheme 75~7).~~’ Their route (A) was more efficient than route (B).

TsOH (dO%lrom A)

HI/ Raney-Ni &OH. AcOH (23%)

0 (f)-217

’

A

> -

(&).217

Scheme 757

B. (R)-6-Ethyl-2-methyl-2,3-dihydro-4H-pyran-4-one 218 (CsHI2O2) This is one of the three major components of the pheromone blend of the male swift moth (Hepialus h e ~ t a ) . Francke’s ~~’ synthesis of (*)-218 is summarized in Scheme 758.958Mori and Kisida synthesized both the enantiomers of 218,

->yy--yr C02Et

acid

0

0

&)-218

Scheme 758

19. Oxygen Heterocycles as Pheromones

369

starting from the enantiomers of ethyl 3-hydroxybutanoate (Scheme 759a).959 The natural pheromone was identical with (R)-218. Another synthesis of (R)-218 was achieved by Jacot-Guillarmod and his co-workers as shown in Scheme 759b. Their synthesis started from the known dithiane alcohol B, which was

-

N a 0 e N 1) & N - C - N d /DMF

1) DHP. TsOH 2) KOH / aq MeOH

on

A C 0 Z E '

100% e.e.

THPO

3)AcOH (96%)

0 3)

0

Si02 chromatog (61%)

TsOH / MeOH

0

(R) -218

[aloni195' (n - penlane)

''''"CT

OH

Similarly :

CO,EI

0

(S)-218

[a],P .193O ( n . penlane)

Scheme 759a

A

6

(51%)

mp 1 1 6 ' ~

1) HgCI,. CaCO,

2) (COCI)l. DMSO) (i.Pr),NEt/ CH,CI,

(65%)

0

(34%)

Scheme 7591,

obtained by the reduction of A with baker's yeast.Io8' Bianchi also reported a synthesis of 218.'088

370

The Synthesis of Insect Pheromones, 1979-1989

C. (2R,SS)-truns-Pityol [truns-2-(1-Hydroxy-l-methylethyl)-Smethyltetrahydrofuran] 219 (CsH,602) This is a male-produced pheromone component of the bark beetle (Pityophrhoruspityogr~phus).~~~ A synthesis of (f)-219 by Francke et al. (Scheme 760)794

-

1) Esletificaron

Catalytic hydrcgenalwn

(1;;7.C02H

2) M e w (+)

- 219

Scheme 760

was followed by the synthesis of both the enantiomers of 219 by Mori and Puapoomchareon by thallium(II1)-catalyzed cyclization of the enantiomers of sulcatol 174 (Scheme 761).728The natural pheromone was shown to be (2R,5S)-219 by GLC analysis and bioassay.794

-

C N d e : quant. aher chromatog a

(S) .174

disln 12%.

TI (OAc),

Similarly : ( R ) - 174

HBF,

.aq h!e,CO

1

after chromatog 70% affer disln 27%

Scheme 761

1

(2R.5S) - 219

[alo2'+18.20(CHCI,)

(2S.5R) - 210

[a]Dn5-17.50(CHC13)

D. cis-Pityol [cis-2-(l-Hydroxy-l-methylethyl)-5methyltetrahydrofuran]220 (C8H,602) This was isolated by Francke as a volatile compound from the elm bark beetle (Preleobius v i r r ~ t u s ) .Vanadyl ~~~ acetylacetonate-catalyzed oxidation of the enantiomers of sulcatol afforded the enantiomers of 220 as the major products (Scheme 762).

"'

19. Oxygen Heterocycles as Pheromones

(5)-174

(23%)

371

(2S.55).220 ( ~ ) ~ ~ .zo~(ctici,) ~ + i i

Scheme 762

E. (3R,6S)-cis-Tetrahydro-2,2,6-trimethyl-2H-pyran-3-ol 221

(CBHIbo2)

This is a pheromone component of the bark beetle ( P . v i t r a t u ~ ) . Two ~~~'~~~ enantiomers of 221, together with the enantiomers of the rrans-isomer 221', were synthesized by oxymercuration-oxygenation of the enantiomers of sulcatol (Scheme 763).963By testing all of these isomers against P. vitrafus, (3R,6S)-221 was shown to be the natural pheromone.962

(S)- 174

1) Hg(OAc),/aq THF

.+IHgCi

2) NaCl

.#a41

(83%)

NaBH, 02/DMF

' (3R,ffi)~221(13%)

(3S,65)-221'(22%)

F, 2,3-Dihydro-2-isopropyl-2,5-dimethylfuran222 (C9H160) This is a sex-specific compound in females of the polyphagous beetle (Hylecoetus dermesfoides).9a A single-step synthesis of (*)-222 was reported by

372

The Synthesis of Insect Pheromones, 1979-1989

Scheme 764

Redlich et al. by a Grignard reaction followed by acidification (Scheme 764).y65 Redlich's synthesis of (S)-222started from D-glucose (Scheme 765).y65,966 The

OH

Ulose derivative

o-Glucose

Lo (90%)

Raney - NI EOH (97%)

CrO,.ZC,H,N

\

'

>

1) Ph,P=CH,

oh

wrm HCI .AcOH (41%)

'

1) TsCl/ C5H5N

2) H2/ Pd-C EOH-AcOH (78%)

>

(67%)

9 2

Raney-Ni (59%)

% 'I'

OH

-H,O

(5).222

[ulDn-l1" (pentane)

Scheme 765

synthetic (S)-222 was reported to show [a]i3- 1.1 " ( ~ e n t a n e ) . ' ~ ~Mori . ' ~ ~et al. synthesized both (R)-222 and (S)-222, starting from (S)-2,3-epoxy-2-isopropyl- 1-propanol A, which was prepared by the Sharpless asymmetric epoxidation (Scheme 766).y67Their (R)-222 and (S)-222 showed [aIDvalues of -8.6" and +9.3", respectively, in pentane. These values were different from that reported for (S)-222 ( - 1.1") by R e d l i ~ h . ~Mori ~ ~ et " ~al.~ then converted (R)-linalool to (R)-222 to confirm the levorotatory nature of (R)-222 (Scheme

19. Oxygen Heterocycles as Pheromones

TcHo> 40% CH20 aq

Me,NH,CI (55%)

UAIH, 9 C H O

(84%) €50

OH

>

L-(t).DET I-BuOOH Ti(OPr'),

373

>

(56%)

(88%)

(RkB

I

(95%)

0,/ PdCI,-CuCi DMF-H,O

Similarly : (S)-B

CaSO,

>

dibtilln (21%lrom 8) [aIDn+4.16'(penlane)

>-

(R)-222

[a],n4.60(pentaw)

*-+& [aJon.552' (penlane)

(5).222

[ U J ~ ~'3 + Q(pentaw)

Scheme 766

767).967The product thus obtained showed [a]? -8.1 (pentane). Therefore, the specific rotation values reported by Mori should be regarded as the correct ones. O

>(R)-Unalool (92.4Ke.e.)

1) TsCl I C,H,N

EbO

(86%)

+

t .BuOOH

OH

VO(acao),

CeHe (5%)

RuCI, - NalO,

(80%)

1) LiOH

+O A

3) MeLi I

EGO

374

The Synthesis of Insect Pheromones, 1979-1989

G. 10-HomonerolOxide 223 (C, IHl,O) This is a volatile signal from an ant-lion (Grocus bore). Baeckstrom et al. synthesized (f)-223and found the natural product to be racemic.”’ Their synthetic route is shown in Scheme 768.3’y

H. (2S,3R,l’R)-Stegobinone [2,3-Dihydr0-2,3,5-trimethyl-6-(1’methyl-2-oxobutyl)-4H-pyran-4-one] 224 (C13H2003)

This is one of the two sex pheromone components of the female drugstore beetle (Stegobium paniceum).y68One year after Kuwahara’s structural proposal, two groups independently announced the biomimetic synthesis of a diastereomeric mixture of 224.y6y-y7‘ Scheme 769 illustrates Mori’s synthetic route.y6y~y71 Has-

(6.6%)

(5.8%)

Scheme 769

sner’s route (Scheme 770) is almost the same as M~ri’s.’’~The synthetic (2S*,3R*,I‘R*S*)-224 was bioactive, but the threshold amount was

-

19. Oxygen Heterocycles as Pheromones

pg, while the natural pheromone was active even at doses of 3 2eqLINPt

HF

0

0

(74%)

(2S'.3R'.l'R'S')-224

0

x

1)3eq UNPt2 t.!aCHO 2)HCI-MeOH

pg.

375 970,97 I

'

(2R',3R',l'R'S').isomer

Scheme 770

Ono's improved synthesis of (2S*,3R*, 1'R*S*)-224 (Scheme 771) was far more efficient than the biomimetic syntheses.972

Scheme 771

To clarify the absolute configuration of the natural stegobinone, both Hoffmann et al. and Mori et al. worked on the synthesis of 224. The first stage was to determine the absolute configuration of 224 at C-2 and C-3. Both groups adopted the same strategy on the basis of the above-mentioned biomimetic synthesis of 224. It was to acylate 4-methylheptane-3,5-dionewith (2R,3S)- and/ or methyl (2S,3R)-3-hydroxy-2-methylbutanoate, or its equivalent. Hoffmann et al. prepared the required hydroxy ester by the asymmetric synthetic method employing (2)-crotylboronate (Scheme 772).973.974 By comparing the CD spectrum of the synthetic (2R,3S,1 'RS)-224, especially in the 350 nm region, with that of the natural stegobinone, the latter was concluded to possess 2S,3R-absolute configuration. 973. 974 Starting from the enantiomers of tartaric acid, Mori et al. synthesized both (2S,3R, 1 'RS)-224 and (2R,3S, 1'RS)-224 (Scheme

376

The Synthesis of Insect Pheromones, 1979-1989 1 ) MeCHO

Me,N MezN:BA

(loo%)

>

%;Bfl N(CHzCHzOH),

\'

2) A&l/ C,H,N (61%)

Scheme 772

(2S.3R.1'RS)-224

(2S,3S, 1 'RS).isomer

[u],= -129' (CHCI,) Similarly:

C0,H (-).Tartaricacid

+ (2R.3S.l'RS). 224

[a),22 +121° (CHCI,)

Scheme 773

19. Oxygen Heterocycles as Pheromones 0 +Co2E,

377

Same as in baker’s yeas1 sucrose

A C 0 2 E 1

(59%)

>95% e.e. el C-3

Scheme nz

4[ 4,] ,

(ZS,3R,l’R).224 [a], not reparled

4-

HPLCs:psrarion

(2S,3R,l’RS).224

Epblegobinone (X-ray) m.p. 4 6 4 O C

[a], not reporled

Scheme 774

773).97’ Mori’s synthetic (2S,3R, 1’RS)-224 was still less bioactive than the natural pheromone itself. The first synthesis of the natural (2S,3R, 1’R)-stegobinone 224 was achieved by Hoffmann et al. (Scheme 774).974Introduction of S-configuration at C-2 was executed by the yeast reduction of a P-keto ester, and (2S,3R, 1 ‘RS)-224 could be separated by preparative HPLC to produce stegobinone and epistegobinone. Because epistegobinone was crystalline, its structure could be solved by X-ray analysis as 2S,3R, 1 ’S. The absolute configuration of the natural stegobinone was therefore determined as 2S,3R, 1rR.974 The second synthesis of (2S,3R, 1 ’R)-224 was executed by Mori and Ebata with stereocontrol at C-2 and C-1‘ (Scheme 775).”’ Starting from two optically active P-hydroxy esters of microbial origin, two building blocks B and C were prepared and combined. Subsequent intramolecular acylation was followed by cyclization and oxidation to give (2S,3R, 1 ‘R)-224. This synthetic material was more bioactive than (2S,3R, 1 ’RS)-224, although it was less active than the extract of the female drugstore beetle.”’ It was later shown that the addition of (2S,3R, 1 ‘S)-epistegobinone to stegobinone significantly reduces the response of male drugstore beetle.y76Stegobinone is also used as the female sex pheromone of the common furniture beetle (Anobium p u n c t ~ t u m ) . ~ ~ ~

378

The Synthesis of Insect Pheromones, 1979-1989 OH

tiNPr‘ Me1 THF-khPA

/LCo2E1

100% e.e.

(86%)

.Bit

EIti/E 0 (78% f b m A)

i l

-CHO

>

OH

I)DHP,PPTS/CH,CI, 2)LiAIH4/E$0 3)NaH,PhCH2CI 4)TsOWMeOH

OH &C02Et

’

+OCH,Ph

1)DMSO,(COCI),,EI,N Z)(n&),NFITHF (68%)

3

’ Ma2cr0H 97% 0.9.

l)Dh!SO.(COCI),,E$N 2)EILi/E$O

l)&o-.PPTs 2)UAIH, (9870)

(82%)

I) ++Cl.imidszole/DMF

2)PPTSIEDH

OH

RuCI~,NalO,/CCl,-MeCN phosphatehutfer

(84.5%)

>

(pH7)

(9W

C

I)UN(SiMe,), % ,%,$

B tC DMAP/C,H,

THF-~,N(CH,),NMe, 2)CICH2C02H-aqTHF 3)HFlaqMeCN 4)DMSO,(COCI),.E$N/CH2Cl2 ( 14%)

(2S.3R.1’R)-224 [a],” -282’(CHC13)

Scheme 775

I. (2S,3R,lfS,2S)-Stegobiol [2,3-Dihydro-2,3,5-trimethyl-6-(2’hydroxy-l’-methylbutyl)-4H-pyran-4-one] 225 (C 13H2203) This is another component of the female-produced sex pheromone of the drugstore beetle (Stegobium p ~ n i c e u m ) . ~ ’ ~ Mori and Ebata synthesized 225 by the route similar to that employed for the synthesis of stegobinone.”’ As shown in Scheme 776, methyl (S)-3-hydroxypentanoate A was one of the starting materials. The ester A was converted to B and coupled with the known hydroxy ketone C’” to produce an ester D. This ester D was submitted to intramolecular acylation, cyclization, and deprotection to give 225, which was identical with the natural

19. Oxygen Heterocycles as Pheromones

LiN(SiMed2

,

379

I ) CICH2COzH/aq THF

D

Scheme 776

J. (2S,3R,l'R)-Serricorone[2,3-Dihydro-2-ethyl-3,5-dimethy!-6-(1'methyl-2'-oxobutyl)-4H-pyran-4-one]226 (CI4Hz2O3)

This is a female produced sex pheromone component of the cigarette beetle (Lasioderma ~ e r r i c o r n e ) . ~Its ~ ~ synthesis ,~~' was accomplished in the same manner as stegobinone. A diastereomeric mixture of the racemates was prepared by Chuman et al. (Scheme 777).980*98' The natural serricorone was shown

380

The Synthesis of Insect Pheromones, 1979-1989

to be (2S,3R, 1 'R)-226, by a synthesis starting from the enantiomers of methyl 3-hydroxypentanoate (Scheme 778).982 OH &CO,Me

e5 Scheme 382

OH

0

(4R,SS)-SitophiIure ESNITHF

2)CBH,.DMAP

,

(90%)

A see

Scheme 776

(ZS.3R. 1 'R)-226

[a]? -26Q0(CHCI3)

Scheme 778

K. (2S,3R,l'S,2'S)-Serricorole[2,3-Dihydro-3,5-dimethyl-2-ethyl-6(l'-methyl-2'-hydroxybutyl)-4H-pyran-4-one] 227 (CI4Hz4O3) This is also a female-produced sex pheromone component of the cigarette beetle (Lasioderma ~ e r r i c o r n e ) . ~A~ diastereomeric '.~~~ mixture of the racemates was synthesized by Chuman et al. (Scheme 777),980*981and the natural (2S,3R, 1 'S,2'S)-isomer was synthesized by Ebata and Mori (Scheme 778).982

L. (1R,2S,4S,7R,10S)-9,lO-Epoxytetrahydroedulan(1,6,6,10-Tetramethyl-3,11-dioxatricyclo[5.4.0.0z~4]undecane~ 228 (C I 3H2202) This is the main component among the volatiles from hairpencils of male monarch butterflies of the genus Euploea such as E. klugii, E. boisduvalii, E. leucostictos, E. tulliolus, E. mulciber, and E. eusipites. Enantiomerically enriched a-ionone was converted to 228 of 19 f 3 % e.e. by Francke et al. (Scheme 779) ,983

M. (1R*,3S*,6R*)-1,3,7,7-Tetramethyl-2-oxabicyclo[4.4.0]dec-9-en-8one 229 (CI3H2,,O2) This was found in hairpencil extracts of the monarch butterfly (Danaus plexippus). Francke et al. synthesized enantiomerically enriched 229 as shown in Scheme 779.983

20. Acetals as Pheromones

381

(1 R.3S.6R,)-228

Scheme 779

20. ACETALS AS PHEROMONES Many acetals have been isolated as pheromones. Bicyclic acetals with bridgedring systems will be treated first, followed by a discussion of tricyclic acetals. The NMR and mass spectral data of several 6,8-dioxabicyclo[3.2. lloctanes were recorded by Mundy et

A. (lS,SR)-Frontalin(1,5-Dimethyl-6,8-dioxabicyclo[3.2.l]octane) 230 (C*H, 4 0 2 ) This is the female-produced pheromone of the southern pine beetle (Dendroctonus frontalis), and the male-produced pheromone of the western pine beetle (Dendroctonus brevicornis). The Douglas-fir beetle (Dendroctonus pseudorsugae) also uses 230 as a pheromone component. D. frontalis and D. pseudotsugae seem to possess enantioselective acceptors on their pheromone receptor cells .985, 986 (1) Syntheses of (*)-Frontalin

Nine additional syntheses of (*)-230have appeared since 1979. A full paper was published describing Sato’s synthesis of (-f)-230 by irradiation of heptane-

382

The Synthesis of Insect Pheromones, 1979-1989

2,6-dione in methanol with quartz-filtered light in the presence of titanium(1V) chloride (Scheme 780).987Sum and Weiler used their dianion alkylation method nCl,

-

I MeOH C H p , (7-8 :3-21

hv

’ &) 230

(76.85% mde yield) (58% distilled yield)

~

Scheme 780

to develop an efficient synthesis of (*)-230 (Scheme 781).988 Noteworthy is

BF,-ECO CH,CI, (95%)

’

heat

(88%)

A

2MoC (85%)

Scheme 781

the facile thermal decarboxylation of A to give (*)-230. An interesting synthesis of (+)-230 was achieved by photo-induced decomposition of bicyclo[3.2. llendoperoxide A, which could be prepared in two different manners (Scheme 782).989This synthetic work was followed by bioassay of the endo-

Scheme 782

20. Acetals as Pheromones

383

peroxide A and azoalkane B. Electroantennogram (EAG) studies of A and B revealed them to be bioactive against D. brevicornis, as is (i-)-230 itself.’” Utaka et al. converted 2,6-dimethylcyclohexanoneto (f)-230 (Scheme 783).’”

Scheme 783

Joshi’s synthesis of (+)-230 started from ethyl levulinate or 4-penten-1-01 (Scheme 784),’” while Serebryakov prepared ( &)-230 from mesityl oxide (Scheme 785).992Imamoto’s simple synthesis of (*)-230 was based on the

-

OH

TsOH.

l)MrCWE$N-CH,CI, ?)LiBr/Me,CO (79%)

& n o

0

l)Ac,O/C,H,N

1)TsOH.

Z)Hg(OAo),,Jones Me,CO (65%)

[g;

’

>

-0‘

*CO,EI 1)MgJTHF

0

PhC03HICH2Clp

(want)

2)Ac2011HF (71%)

O

u

’

(85%)

>

%,Me& (88%)

Scheme 785

0 n 6

dll H SO, TI& (77%)

Scheme 784

H,PO,, 14OoC

>

(75.80%)

o n

n

0

OH con

P)LiAIH,

>

Ph,P=CH,

THF (77%)

>

-&&

(fb230

’

384

The Synthesis of Insect Pheromones, 1979-1989

hydroxymethylation method using samarium(I1) iodide (Scheme 786).993The

Scheme 786

synthesis of (f)-230 by Hagiwara and Uda (Scheme 787) used the cross-aldol

A*

+

A O T H P (59%)

Scheme 787

condensation of the lithio-enolate of 4-(t-butyldimethylsilyloxy)-3-penten-2-one with a protected o l - k e t 0 1 . ~Kongkathip ~~ et al. synthesized (*)-230 from ethyl acetoacetate in five steps involving cyclization with palladium catalyst (Scheme 788).995

'

1) NaOEl IElOH C0,Et

2) KOH / E O H 3) dil H z S 0 4 (71%)

0

Me,sbrNaHIDMSO' (55%)

Scheme 788

(2) Syntheses of the Enantiomers of Frontalin

Since 1975 when Mon synthesized the enantiomers of 230 for the first time, many enantioselective syntheses of 230 have been reported. Fifteen different syntheses of the enantiomers of 230 have appeared since 1979.

20. Acetals as Pheromones

385

In five syntheses, sugars and a-hydroxy acids were employed as the chiral building blocks. A full paper of the synthesis of the enantiomers of 230 from D-glucose was published by Fraser-Reid and his c o - w o r k e r ~ As . ~ ~shown ~ in Scheme 789, they prepared A from D-glucose, from which the diastereomeric

OCH,Ph

’

1) NaH.PhCH,CI I DMF

2) dil H,SO,dioxene OMe 3) Ac,O-BF,*E~O

OAo

B

Na104,NaHC0, aqdioxane

’

PhCHz$--LMe

PH2

CHO

OMe

1) P h F H C O b

Ho-A-MB

2)HplPd Me

C

( 1 S,5R)-230 b l o ” -50.7’ (CHCI,)

(1R,5S)-230

[,IDn

t51.3’ [CHCI,)

Scheme 789

tertiary alcohols B and C were synthesized. Subsequently, B yielded (1S,SR)-230, and C furnished the (lR,SS)-isomer. They also recorded an alternative and a more efficient synthesis of (IS,5R)-frontalin (Scheme 790).”‘

386

The Synthesis of Insect Pheromones, 1979-1989

Monneret and co-workers started from lactose (Scheme 79 1) and synthesized

Lac'ose

I)Ce(OH),-H,O 2)Me,CO.H'

>

"Ao

1)TsCVC5H5N 2)Nal/MeCOEf (62%)

lsosaccharinoiaclone OTs

A

0

"A0

H4Pd.C Ef,N/MeOH (97%)

>

OTs Arnberiysf-15

CHCI,

OK"

(95%)

B

(n.Bu),NBr (8046)

5 ' uH.Ph &,, OCHZPh IjUAIH, 2)OdMeOH Ts 3)Me2S

OHC&°CH2Ph

6H

(59%)

Ph3P=CHCOMe (86%)

H4Pd.C MeOH

6H

>

,,,I..

(80%)

(1A.5Sj430

lalorn+5Z0[ElzO)

Scheme 791

both the enantiomers of 230.997.998 However, these syntheses starting from sugars are too lengthy. Monneret's intermediate B (Scheme 791) was later synthesized by Ohira et al. from D-glyceraldehyde acetonide (Scheme 792)."' The key-step was the intramolecular insertion of carbene into the C-W bond adjacent to the protected secondary hydroxy group (A -+ B). Barner and Hubscher employed (S)-citramalic acid as their starting material and synthesized (lS,5R)-230 (Scheme 793). IWo Naef and Seebach began with the enantiomers of lactic acid and efficiently synthesized both enantiomers of 230 by applying their principle of "self-reproduction of chirality" (Scheme 794). loo' Out of seven chemical asymmetric syntheses o f 230, three utilized asymmetric carbon-carbon bond formation reactions. Sakito and Mukaiyama synthesized the enantiomers of frontalin by an asymmetric Grignard reaction employ-

20. Acetals as Pheromones 0 ?

0

1) OsO,.Na10, l a q THF 2) (n-Bu),NBH(OAc),,CH2C12

________j 3) TsCl I C,H,N

2) POCI, I C,H,N

0

(58%lrom A )

3'

(41%)

(92% e.e.)

Ph

Scheme 791

(Me0)2PCH2COMe K2C0,/aq THF

(1 S,SR)-230

C (= E of Scheme 791)

(32%)

Scheme 792

OHC

HO

HO,C

1) BH, *Me,S I B(Ohk),*THF

2) Me,C(OMe),,Me,CO

(S)-Citamalio add

Ph,P=CHCOMe THF,heat (74%)

'

>

TsOH,CuSO, (48%)

CrO,*C,H,N*HCI

$7

-%"

(92%)

Scheme 793

CH,C12

387

388

The Synthesis of Insect Pheromones, 1979-1989

4

UAIH, E$0

(93%)

>

:

1

Ho

TsOH we1 elher

(97%:73% overall)

Ho

>

..

(lR.5Sj.230 [a]? +53.45'(EhO)

Scheme 794

ing (S)-2-(anilinomethyl)pyrrolidine as the chiral auxiliary (Scheme 795). Ioo2

(63% horn A)

A

Similarly: OH

(91%)

(1S.5R)-230

%

FNPh

COZMe

[aloB.45.5'(E$O)

Scheme 795

By using (R)-&phenylmenthol as the chiral auxiliary, Whitesell and Buchanan prepared both the enantiomers of 230 (Scheme 796).Iw3 Ohwa and Eliel reported two asymmetric syntheses of 230, the shorter one consisting of four steps and the longer of seven, employing chiral 1,3-0xathiane precursors (Schemes

20. Acetals as Pheromones

1) O,/CHZCI,

(60%)

(lS,5R).Z30

[aID-54.8O( ~ $ 0 )

2CrO 'C H N

H

UCIO,/E$O

389

MeMgBr / EhO

CH2C12

-7BOC

(34% aHar HPLC sepn)

A

(34% from A)

Scheme 796

797 and 798).'OO4The lengthy route yielded products of higher e.e. (96%)than the shorter one [(-)-230:70% e.e.1.

U

-

& O F

1) NCS , AgNO, 2) NaBH,

THF,-78'C 2) chromalog.

(60%)

(85%)

.

1) TsOH H20

CH,CI, 2) chromatog. (84%)

(1 R,5S)-230

(91% 8.8. )

-w (89%)

(lS,SR).230 (70% e.8.)

Scheme 797

u

-

The Synthesis of Insect Pheromones, 1979-1989

390

1) 5% HF I MeCN

-

2) CtO,.C,H,N.HCI CH2C12 (72%)

[ 98% d.e. ]

OH LOH .PPTS/C6Hs

1)

3) NeBH, (59%)

.

1) TsOH H 2 0

2) NCS , AgNOJ

k

0 0

U

CH2C12 2) ohromslog.

( 1 R.5S)-230

(96% e.e.1

(84%)

( 34% overall )

( I 5,5R)-230

(96% 8.8.)

Scheme 798

The Sharpless asymmetric epoxidation was applied in the four enantioselective syntheses of frontalin. Meister and Scharf epoxidized methallyl alcohol A to (R)-B (Scheme 799). Ioo5 The unique feature of their synthesis was the carbon-

x

OMe OM@ X./\CO,Me

I-Bu00H

Lewatil SC104 (H')

TiIOPr'), D-(-)-DET/ CH,C12 (32%)

A

1

:

(70%)

1

(n-Bu),SnH

1) KOH I MeOH

2) n c i (89%)

CHz%

m.p. 1o9.i1loc

(6 164%)

Br

m.p. 66-69'C

heat

(UW

(lS,5R)-130 [a]028 -53.6' (E40) ( 297% e.e.)

Scheme 799

carbon bond formation (cis-C -+ D) ajier the formation of the acetal ring. Scharf and his co-workers later reported an improved synthesis along this line using phenylsulfone as the readily removable activator (Scheme 800).'ol Lee pre-

20. Acetals as Pheromones

trans-C

CIS4

1

391

[a]o" -49 4'(E$O)

1

(lR,5S)-230 (a]Dn+50.60 (EI,O)

Scheme 800

pared both the enantiomers of 230 by epoxidizing A to give B (Scheme 801), Ica7

(good yield )

X O

M

( 92% )

A

UAIH,

0 o

H

ECO

HO

H,O

- pntane -

( lS.5R ) 230

B

[alDn- 51.8' (EbO)

( 2 95% e.e. 1

Similarly :

(67% over all ) ( 1R.5S ) -230 [alD2'+52 4' ( E ~ )O

A

Scheme 801

in which the use of a bulky acetal group was necessary. If the corresponding ethylene acetal was epoxidized, both the chemical and asymmetric yield dropped remarkably.Irn7 Yadav et al. (Scheme 8O2),'Oo8as well as Murahashi and coworkers (Scheme 803),Ioo9 employed the asymmetric epoxidation to prepare 230. In Murahashi's synthesis, the palladium-catalyzed intramolecular acetalization was also worthy of note. Ioo9

392

The Synthesis of Insect Pheromones, 1979-1989

( 90 % )

(85%)

TaOH

I.Bu00H E P

L-(+)-DIPT CH2CIZ

(lS,5R).230 [a]:5 -51.5' (E$O)

(85%)

(80%)

(80%)

Scheme 802 PdCI,,

biglyme , 5OoC

THF, -78OC

D-(-)-DET CH,CI,

Cucl , 0,

(ED/.)

( 76 % )

[a]," -50.8' (92% 8.8. )

(44%)

Similarly :

OWOH

__f

(1S,5R)-230

(€60)

v o a , (lR,5S)-230

(83%8.8. )

Scheme 803

Biochemical reactions were used by three groups for the preparation of the enantiomers of 230. Fuganti et al. reduced a-methylcinnanaldehyde with baker's yeast to give A. This was converted to B, to which was added a Grignard reagent to selectively produce C (Scheme 804). ' O ' O Conversion of C to (-)-230

HO OH

HdPd-C 2) NaBH, / E O H (77%)

(65%)

(lS,5A)-230 [a],g-450(E$0)

Scheme 804

20. Acetals as Pheromones

393

was a routine process. Sat0 et a1 reduced 0-keto thiol ester A to give a hydroxy ester B, which was converted to -)-230 (Scheme 805). 'O" Ohta et al. achieved

$'

0 0 &L bakers

__3 yeast

suuose (88%)

A

NaOMe

Ll

MeOH

B (>96%e.e.)

+ MCPBA (82%)

pJ 0

,

OH

1) LiNPr',

-

2) chromalog. sepn.

(94%)

9)+hot; ".,/ C0,Me

(Qw

>

(86%)

TsOH

,,.&0##,,

EhO

(69%)

(lS,5R)-230

[a],n -51.7' (ESO]

Scheme 805

kinetic resolution of (*)-A on incubation with Pichia miso (yeast) to give (S)-A, which was converted to (-)-230(Scheme 806). ' O i 2 1 ) Me,SiCN,Znl,/ CH,CI,

Pichia miso glucose.pH 7 2

(*).A

(63%)

EI,O

2) DHP,TsOH

(66%)

(62%)

Me,C(OMe),

Me,CO,TsOH

B

(88%)

1) Hg(OAc),/ aq THF 0

2) NaBH, / NaOH ,"OW

( 1 S.5R)-230

.50.4' (EI,O)

@)-A

I ) KOH / ElOH CN 2) dll.HCl,pH 1

I ) TsOH / ElOH

-

30°C, 2 days (32%)

Scheme 806

L^_

n,

The Synthesis of Insect Pheromones, 1979-1989

394

B. (lR,5S,7R)-exo-Brevicomin (exo-7-Ethyl-S-methyI-6,8dioxabicyclo[3.2.l]octane) 231 (C9HI6O2)and (lR,SS,7S)-endooctane Brevicomin (endo-7-Ethyl-5-rnethyl-6,8-dioxabicyclo[3.2.1] 232 (C9H1602) exo-Brevicomin 231 is the aggregation pheromone of the western pine beetle (Dendrocronus brevicomis) and the western balsam bark beetle (Dryocetes confusus), while endo-brevicomin 232 is the pheromone of the southern pine beetle (Dendroctottus frontalis) and Dtyocetes autographus. The aggregation response of D. frontalis to entrap when baited with frontalin can be enhanced by (lR,5S,7S)-(+)-232,while (lS,5R,7R)-(-1-232 significantly reduces the beetle response to frontalin. ''I3 Due to the presence of contiguous chiral centers at C-1 and C-7, both 231 and 232 are the favorite targets for chemists engaged in stereoselective synthesis, and, therefore, over 50 syntheses of 231 and 232 have been published since 1979.

( I ) Syntheses of Racemic Brevicomins

The classical strategy to control the relative stereochemistry between C-1 and C-7 is to introduce the diol system by stereospecific epoxidation or hydroxylation of the E- or 2-double bond. Accordingly, the preparation of the geometrically pure olefinic ketone (or its equivalent) has been pursued. Sum and Weiler synthesized both (+)-231and (f)-232(Scheme 807), employing the dianion

< 0

)C , 02Me

((!a%)

BF;E120

CH,CI,

(92%)

Br

---+ c 0 c

KOH

H

H

(87%)

0

&co2Me

H

(fk231

B

V NaH,n-BuLil THF

A

(87%)

aq MeOH

(95%)

0

MCPBA

-./7l& NaH.n-EuLLilTHF

0 +EM"

0

Scheme 807

MCPEA

,&,&C02Me

20. Acetals as Pheromones

395

alkylation as the key chain-elongation reaction.988 Noteworthy is the cyclization step (A B and C D) because it was totally stereospecific in these two cases. A number of earlier syntheses of (+)-231 and (+)-232 involved a thermal or acid-catalyzed cyclization of an epoxy ketone to generate the acetal, often as an exo-endo mixture. Normant's organocopper chemistry was employed for the synthesis of (f)-231 (Scheme 808)."' Mikami and Nakai syn-+

+ 2

EhCuU

-+

'

ou7

HCECH

-

/ THF,HMPA

(sza)

0 -

1)MCPBA 2)H30*

Scheme 808

thesized (+)-231 by the application of the tandem [2.3]Wittig-oxy Cope rearrangement (Scheme 809).''I4 Classical acetylene chemistry coupled with the

3

n.BulilTHF,

0 -

3

?.

-85%

45 h (62%)

(76%)

1 ) MeLi / THF ____j 2) CfO;C,H,N HCi CH,Ci,

>95% E

(70%)

(f)-231

Scheme 809

use of tosylmethyl isocyanide enabled Yadav and co-workers to prepare (f)-231 (Scheme 8 10).lo'' Application of the well-established acetylene chemistry en-

-LiNH, I NH)

7

H, / Pd-CaCO)

-OH

1) MsCl/ Er,N.CH,CI,

2) Nai / Me,CO

(90%)

(95%)

I

TsCH,NC

3U% NaOH,

-NC

-

>

> HO-

-

-NC

(n-h),NOH CH,CI, (70%)

m c HCI

NaH __j Me1 OMSO/ Et20

hexane.quinolina

MCPBA

Y -

(80%)

Scheme 810

0

The Synthesis of Insect Pheromones, 1979-1989

396

abled Joshi et al. to synthesize both (f)-231and (f)-232(Scheme 811).99' H, / PdGaCO,

-7 -

0

H

-

W

O

Ph P B r

H E1,N-THF

1) Mg / THF

2) Ac,O (79%)

T 0

(81%)

(87%)

Na

Ph,P Br2

OH

liq. NH, (84%)

2) TsOH (84%) / EGO

2)(77%) Ac20

F

(*).231

>

Br

CH2CIz (81%)

1) PhCOJi

1) Mg 1 THF

H

0

CH,CI, PhC03H> (want)

-m

%OH

Br

CH2CIz

(89%)

'

/#@

H

(*I-232

Scheme 811

Oxy-Cope rearrangement (A

+

B, Scheme 812) was the key-step in Sereby-

- B

(+).A

_____) 1) I.BuOOH.MoOz(acac), 2)

heal

(@m

@

+

At#,,pf n

(f)-232

(*).231

4

:

0

Scheme 812 0

akov's synthesis of (f)-231and (*)-232. 6I'' Grigg and his co-workers were the first to apply the intramolecular Wacker-type reaction in the synthesis of intramolecular acetals, and their full paper on the synthesis of (f)-231 and (+)-232 has been published (Scheme 813),1017in which the 400 MHz 'Hnmr

20. Acetals as Pheromones CO (45alm) Pd(OAc),,Ph,P

@--

\

UAIH, _ j

COP

E1OH.I 10°C

4

20h

397

.

C0,EI

1

E120

(98%)

0 CH,CI,

4

(76%)

:

THF 2) Reaystn.

1

"

(67%)

1

:

(removable afler critylabn)

. 4.1 rhreo : eryrhro = 84:16

.

1

86

(removable by washing w i h waler)

:

I4

Scheme 813

spectra of (+)-231 and (f)-232 are listed. As shown in the Scheme, Grigg's palladium-catalyzed reaction of butadiene with carbon monoxide and ethanol was of low stereoselectivity (4 : l ) , and this fact complicated the synthesis. Jatczak et al. devised a new method for the cleavage of a tetrahydrofuran derivative A (Scheme 814) to give a mixture of B and C, which were separately converted to (+)-231and (f)-232,respectively. '"* (E)-1-Silyl-1-alkene was found to give rhreo-l,2-diol stereoselectively, and Tamao et al. prepared (f)-231(Scheme 815).'OI9 Another silicon-mediated synthesis of both (f)-231 and (f)-232 was published by Hudrlik et al. (Scheme 816).'020 Organosulfur chemistry was also useful in providing (+)-brevicomins, and Ishibashi et al. prepared (+)-231and (+)-232starting from p-chlorophenyl methyl sulfoxide (Scheme 8 17). '02' Oxidative Grob fragmentation of y-tributylstannyl alcohol A to olefinic ketone B was the key step in Ochiai's synthesis of (f)-232(Scheme 8 18) .667

The Synthesis of' Insect Pheromones, 1979-1989

398

(f)-232

Scheme 814

S ,N -iP?,

I

' I

I&OK I n.BuLi

>-

n.hexam.E$O

[

)

&q-NNP?,

i+

n

1) HCI / I-PIOH

0 0

>

-1

EIMgBr.CuCN>

2) MCPBAI CH,CI,

EpTHF

-Si-

.soo

OH

(70%)

137% overall]

0 0-53-

(95%)

I I

30% H,O,KF ___j KHC03 MeOH-THF

(f)-231

Scheme 815

(&).232 C,H,N-H,O-I-BuOH 2) HCI (79%)

Scheme 816

NP8,

(f)-231

20. Acetals as Pheromones

399

(major)

( Be

:

12 )

Scheme 817

6

,&\ 0

+ M

5 /+"\

- - qH l)(n-Bu),SnU/THF

2) Ell I HMPA

,

(69%)

Sn(n-@+

Sn@ (. +

A

DCC.PhI0

BF,E$O/CH,CI, (67%)

,.,.+'\

__3

0

B

&232

Scheme 818

Diastereoselective formation of the 1,2-diol system, the key feature of brevicomin precursors, was attempted by nucleophilic addition of an appropriate carbanion to an aldehyde intermediate. Hoffmann et al. studied the addition of y-alkoxy-(Z)-allylboronates to aldehydes and synthesized (+)-231 (Scheme

400

The Synthesis of Insect Pheromones, 1979-1989

Scheme 819

Similarly but independently, Wuts and Bigelow also synthesized

819).

(f)-231by the same methodology (Scheme 820).'024A y-methoxyallylalu-

H,/ Pd-C ElOH (69%)

x O

4

-

OTHP

wet

€60 (f)431

Scheme 820

minum compound and an aldehyde were chosen by Koreeda and Tanaka as the starting materials for the synthesis of (f)-231(Scheme 821).'025Similarly, the

- n

l)s.Buli/TMEDA

MeO-

2) Et#,lCl

LAIEb 1) G

C

H

2) NaH , Me1 (8%)

(f)-231

Scheme 821

O

(73% overall )

p J + OMe

20. Acetals as Pheromones

401

addition of a heterosubstituted allylic carbanion to an aldehyde was employed by Y. Yamamoto et al. to prepare (f)-231 (Scheme 822).'026(2)-Methoxy-

allylstannane was used by Koreeda and Tanaka to prepare (*)-231 (Scheme 823).'02'

- 1) s-BuLi/ TMEDA

* o q

n

'1 %CHO

~0

2) (n-Bu),SnCI

LS"(".B"),

BF;EhO

(9Wh)

Oh

--$$

1) NaH / THF. Me1 2)

2) MeOH,H,O

H2/Pd-C

Oh

(88%)

(*)-XU

Scheme 823

The third approach to exo- and endo-brevicomin was the ring formation by hetero-Diels-Alder reactions. Cohen and Matz prepared a dihydropyran A (Scheme 824), which was converted to a mixture of (+)-231 and (+)-232via

'

PhS

1) EICHO

2) H,O* (40%)

160°C,lhr

-k

PhS

0

(73%)

THF, -78%

A

-B El

(f)-231i (*)-232 (43 :57)

Scheme 824

B

402

The Synthesis of Insect Pheromones, 1979-1989

a-lithioether ( *)-B.Ioz8 Cohen and Bhupathy then reported a more efficient and simple one-flask synthesis of a mixture of (*)-231 and (f)-232 ( 1 : 4) from acrolein dimer in 69%yield (Scheme 825). Stereoselective addition of ethyl3eq EtLi / E$O Li

LiO

QCHO

(k)-231t (kJ.232 (1 '4)

Scheme 825

metallic reagents to acrolein dimer was subsequently achieved by Cohen to produce (+)-231 as the major product (Scheme 826).Io3O Singh and Oehl-

%

1)Elgn/EhO

(76%)

2) chromalog.

-b

OH

L!WO

erymro ( 5.7

OH

02.5es BuLI/TMEDA

6H

QCHO

H

:

1 )

p

.~. ~

Scheme 826

schlager further studied the chelation versus nonchelation control in addition reactions of ethylmetallic reagents to acrolein dimer (Scheme 827). When

Scheme 827

ethyllithium was used in the presence of boron trifluoride etherate, high selectivity (92 : 8) was observed for nonchelation-controlled addition, yielding the

20. Acetals as Pheromones

403

erythro-product leading to (*)-232.Ethylcopper reagents in the presence of magnesium salts were found to give the threo-product generated by chelation control. ‘03’ Chelation-controlled facially selective cyclocondensation between diene A and a-benzyloxyaldehyde B as catalyzed by magnesium bromide in THF was employed by Danishefsky et al. for their stereoselective synthesis of (&)-231 (Scheme 828).’03* Scharf and co-workers found that the transacetal-

B

A

1) n-BuUITHF-TMEDA

1) Hg(OAc),/ THF

OH

0 E1

2) NaBH, I ElOH (quant.)

3) U / EtNH2+BUOH-THF (50%)

(*).231

Scheme 828

ization between (*)-A and B under kinetic control results in (f)-C. This acetal C was treated with a base to produce the brevicomin skeleton D, which furnished (*)-232 (Scheme 829).’033Another route starting from (*)- A and E was also developed via ( f)-F and ( f ) - G to generate ( f)-232.1033

-Br

1) HzO2 I aq HC0,H ___3 2) ToOH / MeOH

b S 0 , P h

B

T o OHH Br (*).A

(92%)

H (f)-D m p. 139-142OC

-

(53%)

TaOH/CH2C12 & , I week (5W

(f).232

Br

( f )(&isomer ~

only)

m.p. 6144’C

hv (n-Bu),SnH (90%)

Several other syntheses of (f )-231 and/or (33-232have been reported. By employing methoxy(pheny1thio)methane as a homologation reagent, Otera et

404

The Synthesis of Insect Pheromones, 1979-1989

al. prepared a mixture of (*)-231 and (*)-232 (Scheme 830).

Electrolysis

Scheme 830

of hemithioacetal A yielded mixed acetal B, to which ethyllithium was added to construct the brevicomin skeleton. A unique and efficient synthesis of (*)-231 was reported by Sato et al. (Scheme 831), which employed a photochemical

KOH

0

dilH2S04

__j MeOH (51% from A)

94

(kp231

:

6

&.).232

Scheme 831

reaction (A B) and diastereoselective reduction of chloroketone B.'035 (*)-I ,2-Divinylglycol A, a product of the reductive dimerization of acrolein with zinc-copper couple, was converted to (f)-231 (Scheme 832). As shown in Scheme 833, Giese et al. used a radical reaction to construct the carbon skeleton of ( f)-231.'037 An interesting chain-carbonyl transposition strategy was adopted by Wilson et al. to realize a unique synthesis of (*)-231, contaminated with a small amount of (f)-232 (Scheme 834). Another novel and +

20. Acetals as Pheromones

0

OCH,Ph

(94%)

1) CCI,CHO.

Hg(OCOCF,),

(fW

I CH,CI,

2) KLKOH I H 2 0 ; 1, (80%)

(f)-231

Scheme 832 CCI,

+

0x0 I

&

I

(f)-B

(fkC (71

:

29)

1) (n-Bu).,SnH AlBN / toluene

+

2)flashchrornatog.sepn. (50%)

(95%)

(%).23t

Scheme 833 1) Br,.Ph,P / Et,O

(*)-231

(85

:

(n-Bu)pH/loluene (65%)

(fP232

15)

Scheme 834

Me

405

406

The Synthesis of Insect Pheromones, 1979-1989

noteworthy construction of the intramolecular acetal system, as reported by Padwa et al., employed the rhodium-catalyzed cycloaddition reaction of 1-diazo2,5-hexanedione to propanal (Scheme 835).'03'. Ox idative fragmentation of

SiO, chromalog.

HS(CH,),SH Zn(OTI),

2

A

:

1

B

(&)-231

(f)4!32

Scheme 835

y-hydroxystannane A to give the known enone B was the key-step of Kitching's synthesis of ( f)-231 or (+)-232 (Scheme 836).5'2Bartelt and Mundy reduced

B

(f).231 Scheme 836

(f).232

A with triisobutylaluminum to create a mixture of (f)-231and (+)-232(Scheme 837).'04' A thorough investigation of this type of reduction of a carbonyl group

A

Scheme 837

(k)-231t (f)-232 (84:16)

20. Acetals as Pheromones

407

with various reducing agents was made by Ramaswamy and Oehlschlager. I W 2 As shown in Scheme 838, they achieved an efficient synthesis of (*)-231 and (*)-232 by this approach. '04'

c

Cb.0

(*)-232

(exo:enda=8:92)

Scheme 838

(2) Synthesis of Optically Active Brevicomins

A. From Tartaric Acid. Mori's first synthesis in 1974 of the enantiomers of exo-brevicomin 231 started from tartaric acid (Scheme 268, Ref. 1). Since 1979, seven new syntheses of optically active brevicomins have been achieved beginning with tartaric acid. Diethyl D-tartrate was converted by Masaki et al. to (lR,5S,7R)-( +)-231, the bioactive enantiomer (Scheme 839). I W 3 They were

A

8

rnp 8 5 - 8 7 ' ~

(1R,SS,7R)-231 [QI0 41.6' (EbO)

Scheme 839

the first to employ the acetal intermediates in earlier stages to execute the final ring-closure by carbon-carbon bond formation in a later stage (A -+ B). Mori and Seu employed the palladium-catalyzed Wacker reaction for the 1 1-step syn-

408

The Synthesis of Insect Pheromones, 1979-1989

thesis (4.5% overall yield) of (+)-232and (-)-232 from the enantiomers of tartaric acid (Scheme 84O).la4 In another synthesis, Seu and Mori constructed

y &

PdCI, , CuCI, DME (67%)

(1 S,5R,7S)-231

[alDP-73.2' (CHC13) -73.6' (EGO)

Similarly :

CO,H

=g

Q ( 1 A,S,7R)-231 [a],2ot72.1' (CHC13)

+72.4' (€60)

Scheme 840

the carbon skeleton of (-)-231 by alkylating a sulfone A with B (Scheme 841).Iw5 A radical carbon-carbon bond formation reaction (A -+ B) was the

(61%)

flS.5R.7SI-231 IalDn-73.4' (EGO)

Scheme 841

key reaction in Giese's synthesis of (-)-231 (Scheme 842).Ia6 The overall yield in Giese's synthesis was as high as 17%. Achmatowicz and Wicha de-

20. Acetals as Pheromones HO

OH

?I

x0

0

1 ElOH , H' H O ~ C . ~ C O ~ H Me,CO H*>

(75%;

E10,C

L-(+)-Tanark

LiAlH

J!-(

I

CO2E1

409

>

add

A

1) H2/ Pd-C I Ek0 2) TsCl I C,H,N DMAP/CH,CI, (69%)

PhCH,O

>

B

TsO mp 5SoC

(75%) (lS,5R,7S)-231 lalo" 47.7' (CHCI~)

Scheme 842

veloped an interesting synthesis of ( -)-endo-brevicomin (232) from (+)-tartaric acid by using a diastereoselective Grignard reaction with A to give B predominantly (Scheme 843).'047Because B could be converted into C by

u

L.(+)-Tamric acid

Br

+

6

BrG A

chromalog.,

sepn.

8

-'&$#&> (71%)

B

5

H, / Pd.CaCO, EtOAo (7P4

> -

:

6H

c

1

OH

OH

n 0 dilHCKY

> *

0

(91%)

6H

-%

H (iS,5R,7R)-232 (aIDn-79.3' (E$O)

KBH(se@Bu), THF (75%)

(70%)

D

> (lR.SS.7R).231

Scheme 843

0 0

The Synthesis of Insect Pheromones, 1979-1989

410

oxidation-reduction via D, this procedure also constitutes a formal synthesis of (-)-exo-brevicomin (231). Yadav's synthesis of (-)-231 was based on thc rcduction of a dialkylated tosylmethyl isocyanide with lithium in liquid ammonia to the corresponding hydrocarbon (A B) (Scheme 844).93Kotsuki et al. pre+

HO

OH

HOzC,HCO$

(85%)

L-(+)-Tartaric

A

SCM

(COCI), , DMSO ESN/CH,CI, (72%)

'

B

THF (72%) OH

OCSSM

Scheme 844

pared (+)-231 by a coupling reaction between the triflate A and the Grignard reagent B in the presence of cuprous bromide (Scheme 845).'04' It should be noted that the tosylate in A was less reactive than the triflate.

X

Scheme 845

B. From Glutamic Acid. LarchevCque and Lalande synthesized ( +)-exo-brevicomin (231) starting from D-glUtamiC acid (Scheme 846). '04~. Notable features of their synthesis are the stereoselective reduction of ketone G to alcohol B and the two-carbon elongation reaction (C --t D) with a new reagent MeCH(CN)NEt2.

20. Acetals as Pheromones

I ) TsCI / C,H,N

E

1

t

a

*

I

e

(80%)

LiNPri,/ THF-HMPA ') MeCH(CN)NE$ 2) NH,CI aq 3) S O , , CHZCIZ/ HzO

411

,"'m, El

0

0

0

dil H,SO, (95%)

D

(75%)

(lR,5S,7R)-231 [uIDmrW.3' (CHCI,)

Scheme 846

C. From Glyceraldehyde Aceronide. Sat0 et al. synthesized the enantiomers of 231 and 232 starting from D-glyceraldehyde acetonide (Scheme 847). The Me Si

0+

THF-HMPA

A M g B r + OHC&o A

D-Glyceraldehyde acetonide

>

N w k

(86%)

OH

1)HCI 2) H2/Pd.C

(49% horn D)

O+ OH

B

n OCH,Ph

*

+

1

:

1.7

l)PhCH,Br.NaH 2) Chromalog. sepn.

,

c

'

(1S,5R,7R)-232 -93.1' (E40)

(1 S,5R,7S)-231 [a]oz6 -80.3' ( ~ $ 0 )

Scheme 847

(iR.5S.7$)-232 [a]; +96.6' (Eb0)

The Synthesis of Insect Pheromones, 1979-1989

412

&

OH

0 0

x

OCH,Ph NaH/THF-DMSO PhCH,CI ' 0 (88%)

OCH,Ph +

0

K

A 84 : 18 B (Separable by HPLC)

D.Glycaraldehyde acetonlde

1) dil H,SO,.MeOH

(39%)

5

0

4

6H

>*

P'MgBr

OCH Ph

>T

3)Rectysln 2) TsCl/ CsH,N

E;EcHCI,> (92%)

Cul / THF

OH

(75%)

D

C rnp 6969.5'C

1) PhCHZCl INRH

2) 0 3 / CH& 3) PhaP /CH2CI2 (70%)

'

O

0 H

C

S

OCH,Ph

>

Ph3$,;

H2 / P b C

0

(80%)

OCH,Ph

6CH,Ph

x

85

1)H 0' / CH ,N ,

6 OCH Ph

>

:

15

1) Me,CuLi

>

2)H:;F)

o"'

3) NaOMe (59%)

(84%)

punboon

6 OCH ph

x

1) AczO 1 C5HsN DMAP

*)03

OH

3) Ph,P

I

0

A

(40%)

MeOH

OAC

[

1) KOH - MeOH 2) EbO .2N H2W4

overall 10-13%] yield

>

1 ) O ZI N\ OCO,H Ph3P/ THF EtOpCN-NC02E1 2) K$O,/

0 0

(88%)

4) H, I PbC I

(84%)

8;(1 R,5S,7S).232 (>98% e.e.) [.IDm t80.0° (ESO)

0 0

2) TC ;I

0 6

x

>G--fH$f

MeOH - H20

OH

(53%)

+3-

(1S.5R 7#)-23¶ [a(, -59.7'

(E(20)

OH

A

Milsumbuinversion as above (75%)

0 0

x

OH

(lR,5S,7R).231

57%

Scheme 848

[alDm49.3' (EGO)

20. Acetals as Pheromones

413

key-step was the stereoselective Grignard reaction with a-benzyloxy-P-trimethylsilyl-3-butenal D. Mulzer et al. also prepared the enantiomers of 231 and 232 from D-glyceraldehyde acetonide (Scheme 848). The Mitsunobu inversion played an important role in their synthesis. A remarkably simple synthesis of (+)-exo- and endo-brevicomins was achieved by Scheffold et al. (Scheme 849) by employing vitamin B12-catalyzedcarbon-carbon bond formation.36. OH

E C H O ElMgl

0 0

K

3

0

r/0

K

OH +

0 0

K

. .

C

Similarly :

6

=$ (76%)

x

(lR,SS,7S)-232

+& (lR,5S,7R).231

Scheme 849

D. From D-Glucose and Other Sugars. Sherk and Fraser-Reid seven step synthesis of (+)-exo-brevicomin 231 from D-glucose via dimesylate A yielded overall 21 % from A (Scheme 850).'055(+)-exo-Brevicomin 231 was prepared

A

D-Glucc~,

(lR,5S,7R)-131 talon 4 1 . 5 ' (Satvent cot specified)

Scheme 850

20. Acetals as Pheromones

mp 61.M2.5°C

415

(lR,5S,7S)-232 [alnnt79.5' (EI,O) ( 298% e.e.)

L-Arabinow

(1S.5R97R)-232 [alDp-78.9O (~40) (298% e.e.)

(2R.3R)A

Scheme 853

hydrates are rather lengthy processes due to the necessity of removing the extraneous chiral centers of the starting materials. E. By Asymmetric Epoxidation. The invention of asymmetric epoxidation by Sharpless et al. greatly facilitated the brevicomin synthesis. Seven different syntheses of 231 and/or 232 employed this reaction. Johnston and Oehlschlager Ph

H0&OHOH

Dxylcea

* GET 0Y 0 Ph

.lo%

[

0

]

ksEt u' UAIH, OxO

SEI

(28%)

>

L

S

E

0

0

SEl

t

Y Ph

[aIDa+75' ( ~ $ 0 )

Scheme 854

416

i)CH2Ph

The Synthesis of Insect Pheromones, 1979-1989

2) TsOH 3) Prsp.QLC (32%)

(1S,5R,73-232 [a], -79.5' (EI20) (98% e.e.)

(1 R,5S,7S)-232

[a lop +79.8' (El20) (98% e.e.)

Scheme 855

prepared the enantiomers of 231 in 30-40% overall yield as shown in Scheme 856. Io6' Starting from divinylcarbinol, Takano and his co-workers synthesized 0 n 0

UCECH

%cl

THF.HMPA (94%)

>

-

> ow,fioH ow/ > n-Buti/THF

H, / P-2 Ni

(CH,o),

H2N(CH2),NH, MeOH (92%)

(82%)

(1 R,5S,7R)-231

[a]," r59.0' (CHCIJ (95% e e.)

(1 S,5R,7S)-231

-60.6' (CHCI,)

Scheme 856

20. Acetals as Pheromones

417

(-)-231 and (+)-232 (Scheme 857).Io6' In Takano's process, the selectivity of

'+

I ) NaH , (n-Bu),NI PhCHPBr/THF OH

(50aW0)

A

1) MsCl, E\N/CH2CI, 2 ) K 0 2 , 18-Crown4 DMSO

>

(81%)

-

o n

OH

ACHZPh

mH,Ph

1) Li I NH,-THF O.lMHCIO, (56% overall)

6 6

W M g B r

Cul/THF (96%)

'

> (15.5R.7SJZ31 la], a . 5 ' (EbO)

Scheme 857

the epoxidation step was 90 : 10 enantioselectivity and 93 : 3 threo-erythro sclectivity.1°62Mori and Seu synthesized the enantiomers of 232 by the Sharpless epoxidation, followed by chain elongation and the Wacker oxidation (Scheme 858).'063The enantiomers of endo-brevicomin 232 were also prepared by

Scheme 858

Oehlschlager and Johnston (Scheme 859). low Sutherland and his co-workers employed Payne rearrangement in THF of 2,3-epoxy alcohol in their five-step synthesis of (+)-231 (Scheme 860).'065 Scharf et al. synthesized the enantiomers of 231 and 232 by combination of the Sharpless epoxidation and sulfone alkylation (Scheme 861).'Oo6They also prepared the analogs of 231 and 232 with a vinyl group instead of the ethyl group at C-7 by using Sharpless epoxidation and sulfone alkylation.'a66 Yadav et al. synthesized (-)-232 as shown in Scheme 862. Io6'

418

The Synthesis of Insect Pheromones, 1979-1989 1) HCcCCH OH, UNH, THF liq kH,

.

(95%)

(55%)

K

> o

0

O H-

(1S,5R,7R)-232 (alDnot reported (83%e e )

Scheme 859

A

PdCll, CUCI, THF

(31% overall horn A)

(lR,5S,7$-231 [a!, r67.5' (EGO),6 5 . 1 ' (CHCI,) ( Z 95% 8.8. )

Scheme 860

F. By Chemical Asymmetric Reactions Other than Asymmetric Epoxidation. In a synthesis of (+)-231 by Asami and Mukaiyama, ester A was prepared from (S)-2-(anilinomethyl)pyrrolidine, from which B was derived (Scheme 863).'06*Their (+)-231 was found to be of moderate optical purity. (R)-Carvone was used by Wuts et al. to prepare a chiral boronate A, which was treated with aldehyde B to yield C and then (-)-231 (Scheme 864).'069The homologation of chiral boronic esters A and B with dichloromethyllithium was employed by Matteson et al. in the synthesis of (+)-231 (Scheme 865).30'.302 Chong and Mar employed chiral a-alkoxyorganostannane ( R ) - B , which was

(1A,SS,7R)-231

lalon +57.95' ( E ~ o ) (89% e.e.)

(1S,5R,75)-231 [alon -41.go ( E ~ o ) (63% e.e.)

(80%)

.

.

[ 44% overall 1

(lS+5R,7R)-232 (EhO) (88%e.e.)

PIDn65.2'

(1R,fE,7S)-232

laloa -5a.z0 ( E ~ o ) (78% e.e.)

Scheme 861

o n

1)MgITHF z)&CHO'

0 0 -Cl

(W%)

I dn & F

0

(+)-DIPT. Ti(0Pr)'

OH

&

+

[ r+)

t~BuOOHICHZCIz -MOC (30%)

>

(SW 1) NaHlTHF, CIC0,Me (85%) 2) SO2 chromatog.

( 2 : 1)

+

')NaOM/M@H> 2) dil HCI

(75%)

35.5%

-B H

(lS,5R,7R)-232 [a],28-67.50 (ESO)

Scheme 862

419

The Synthesis of Insect Pheromones, 1979-1989

420

A

B

39

:

1

( 6:l In Ihe absenoa of ZnB2)

[Q]ont50.3'

(E40)

Scheme 863

b n

0

1) 0,/ hexam 2) LiAIH,

3)NalO,

A

(R)-Cetvone (94% e.e.)

x

f%

0

O~$,,CHO B

OH

i

0

1)H2/Pd

>

2) H30'

A A

C

' (lS.JR.7S)-131

[u]2' -60.6'

(EkO)

Scheme 864

prepared by reducing A with 2,2'-dihydroxy-l, 1 '-binaphthyl-modified lithium aluminum hydride (BINAL-H), for the synthesis of (-)-231 and (+)-232 (Scheme 866). Koga and his co-workers achieved asymmetric dihydroxylation of A to give (+)-231 (Scheme 867), which is the most direct synthesis of (+)-231.

G. By Biochemical Asymmetric Reactions. Biochemical asymmetric reactions, such as reduction and aldol formation, were used for the synthesis of brevicomins.

20. Acetals as Pheromones

OH

421

flR.S.7Rl-231 lwilh . . 2.3% 232) (a],26 +81.1' (~40)

mp 30-31OC

Scheme 865

1) (S)-BiNAL-H/THF. -78'

0

4%B%

2) MOMCi, (i.Pr),NElICH,CI, (57%)

A (air-sensi(ive)

'

CjMM

-SnBU, (R)-B (98% em)

ca1.7D% HCIO, CH,CI, (75%)

(4-231

(+) -232

[a]$4+S20 (E$O)

a [:]

Scheme 866

-72' (E$O)

422

The Synthesis of Insect Pheromones, 1979-1989

Scheme 867

Treatment of cinnamaldehyde with baker's yeast and D-glucose produces diol A (Scheme 868). Fuganti and co-workers converted A to B. When B was

11 PhCHICl

NaH/DMF

2)50%AcOHaq

3) HIO, (76 5%)

'

PhCHz? 4 C H O

E

C

-

8 : 4

D

PhCHtS)

THF

2). HIO' .

1) H, I PbC 2) pep GLC

( 1 R.S,7R)431 [(I] +70° (EL01

(lS,5R,7S).231

la1.e0W$J)

(15,5R,7R).232 ((11 -76.7' (ELO)

(lR,5S,7S)-232 [a]+74' (ESO)

Scheme 868

treated with ethylmagnesium bromide, a separable mixture of C and D was obtained. @)-Aldehyde E, derived from C,yielded (+)-231and (-)-232,while (R)-E, derived from D,furnished (-)-231and (+)-232in a nonstereoselective manner (Scheme 868).'07* Later Fuganti et al. reported another synthesis of (+)-231as shown in Scheme 869.1073 This synthesis was again nonstereoselective. A unique preparation of the enantiomers of 232 by Ramaswamy and Oehlschlager was based on the yeast reduction of A to generate B, (f)-231, and (+)-232(Scheme 870). The reduction process is an example of kinetic

20. Acetals as Pheromones

x

x

1) chromalog. prrlln.

HO

OH

2) PhCH2CI/NaH

OH

2)TsCl/C5H5N

3) H,O'

OH

1) PhCOCI/C5H5N

OCH2Ph

423

'

(56%)

65-70 : 30-35 PhCOO

OTs

&

KOH

OCH2Ph

OCH,Ph

(70Oh)

1) KBH(s.Bu), 2) PhCH,CI /NaH

OCH,Ph

2) Ph,P-CHCOMe

A

H,/ Pd-C

(352 from A)

PhCH,O

(lR,5S,7R)-231 [a],g t74' (E1,O)

Scheme 869

6

0

3)kl 4) dl. AcOn

B

0

(lS,5R,7R)-232

!Sl%ee)

Scheme 870

The Synthesis of Insect Pheromones, 1979-1989

424

resolution by baker's yeast. Noda and Kikuchi reduced A with baker's yeast to give B, which was converted to ( +)-232 via diastereoselective reduction of hydroxyketone C (Scheme 871). 0

OH

OH

(65%)

HgO, EF3*E$0 aq.THF

'

OH

1) Zn(BH,), / THF

0

(70%)

u

2) d l H2S04 (56%) 3)prepGLC

' (+)-232

c

[a1,2'

(-)-231

(%I)

+ 74.6' ( ~ $ 0 )

Scheme 871

A unique chemoenzymatic synthesis of (+)-231 by Schultz et al. utilized highly stereoselective carbon-carbon bond formation with rabbit muscle fructose- 1,6-diphosphate aldolase (Scheme 872). 0 L

E Y

H

1 ) Rabbit muscle aldolase (90% conversion) 2) Add phosphawe (PH 4.8)

1) Rabbit muscle aldolase (80% conversion) 2) Add phosphatase

LiAIH, OH

0

(90%)

y?r

OH

OH

>

(PH 4.8)

m> ,

1) MsCI/C,H,N 2) Na,

eOH

(44%)

\

K02CN=NC0,K

AcOH (WD/.)

.@

P

(+) -231

1) NaH. CS,. Me1 2) (n-Bu),SnH I C,H,

Scheme 872

C. exo-7-Ethyi-5-methyl-6,8-dioxabicyclo[3.2.l]oct-3-ene 233 (C9H 1 4 0 2 )

Although 233 is not an insect pheromone but a mammalian pheromone, its syntheses will be reviewed here due to its close structural resemblance to 231.

20. Acetals as Pheromones

425

This olefinic acetal 233 is a chemical signal of the male state and a potential multipurpose pheromone of the house mouse (Mus musculus). This compound (f)-233 had been synthesized, even before its discovery as a natural product, as an intermediate of Kossanyi's synthesis of ( f)-exo-brevicomin 231 (Scheme 140, Ref. l)."" Wiesler et al. synthesized (+)-233 starting from (Z)3-hexen-1-01 and introducing the C-3 double bond at the final stage (Scheme 873).'077Mundy and Bornmann prepared a mixture of (+)-233 and its endo-

-

TsCl C5H5N'

0

MCPBA

v-7/\OTP

-0Ts

z2C0 (92%)

'

1) NaOH I eq.EOH 2) HCI 3)Pb(OAc),.Cu(OAc), '5hN

(54%)

--/

(f) -233 Scheme 873

isomer by using organoselenium chemistry (Scheme 874). loB0 Diastereofacial

ero:md0=60:40

(+) -233

+ lk endo-isomer

(60 : 40)

Scheme 874

control in the cyclocondensation reaction was the key to Danishefsky's synthesis of (+)-233 (Scheme 875).10321 l o * 'The cyclocondensation was followed by

0&OH

"

1) (i-&I)fiIH / C,H, El

2) Hg(OAc), / THF

HO

A

Scheme 875

El

426

The Synthesis of Insect Pheromones, 1979-1989

mercuric-ion-initiated acetal formation, and the resultant a-mercuriocarbinol was treated with methanesulfonyl chloride in triethylamine to effect olefin formation. Bhupathy and Cohen prepared (+)-233 by means of organoselenium Acid-catalyzed intramolecular opening of an epoxchemistry (Scheme 876).

1.Egn

[ +]

f & +

EhO

O C H O

OOC-r.1. (76%)

n-BuLi/TMEDA

OH

&I

2. chrnmaIop.sepn.

5.7

Me1 / EheTMEDA ( 76% )

1

Scheme 876

ide by a carbonyl group was the key reaction of Wasserman's synthesis of (f)-233 (Scheme 877). ' O S 2

( 67% )

H,/tindlar-Pd quinoline/CH,CI,,

+(

(55%)

+ 11% 01 (f) -233

&. 233 Scheme 877

Three different syntheses of the enantiomers of 233 were reported. The relationship between bioactivity and absolute configuration of 233 is not yet known. In Wasserman's synthesis, the Sharpless asymmetric epoxidation was employed (Scheme 878).Ios3Mori and Seu started from tartaric acid and employed organoselenium chemistry for the introduction of the double bond (Scheme 879).IoE4Masaki et al. also synthesized the enantiomers of 233 by beginning with the enantiomers of tartaric acid (Scheme 880). IoE5

20. Acetals as Pheromones TilOPA.

( 42% )

(9 5 i )

crO ' co N'HC' o l

HO

n.BuLi/THF

H2'Pd-CaC03

I%%)

(45%)

[ulon

Similarly :

- 70.5'

(EGO)

( lS.5R.7S ) I 233

[a],n c 70.4' (EhO)

Scheme 878

PdCI,,CuCi, C0,H

meme 840

NaHCO,/ DMF' ( 84% )

(CH2),CH=CH,

Me,SiCI

O

A

Ei3N/ DMF' reflux

PhSeCl CgHgN CH2C12 /

( 86% )

>

minor

ebPh

major

20,"e:

( 70% lrom A )

MCPBA

( 48% )

( lS,5R,7S ). 233

[a]~+9i.5'(CHC13) (ca. lOOo/Oe.e. )

Similarly :

CO,H

(iR,5S,7R) - 233 [a]? -90.5'( CHCI,)

Scheme 879

+

427

428

The Synthesis of Insect Pheromones, 1979-1989

(lS,5R,7S)-233 [a),20+72.0° ( CHCI, )

Similarly:

COzH

(lR,SS,7R) -233

Scheme 880

D. (lS,2R,4S,5R)-~-Multistriatin (2,4-Dimethyl-5-ethy1-6,8dioxabicyclo[3.2.1]octane 234 (C,,H

This is the pheromone of the smaller European elm bark beetle (Scolyfus multistriatus). Since 1979 several new syntheses of (&)-234have been published. Bartlett and Myerson's synthesis of (+)-234started from rneso-2,4-dimethylglutaric anhydride, and utilized a highly stereoselective iodolactonization reaction (A -+ B) to fix the relative stereochemistry of the third chiral center (Scheme 88 1). Io9' Marino's organocopper chemistry enabled him to prepare (+)-234stereoselectively (Scheme 882). The noteworthy step in the synthesis of (+)-234by Walba and Wand was the diastereoselective ( > 95%) addition of lithiothioformaldine to aldehyde A to create B (Scheme 883). In connection with a synthesis of (f)-234,C (Scheme 883) was reported to be bioactive as an analog of a-multistriatin.'094Serebryakov et al. reported a synthesis of a mixture of multistriatin isomers as shown in Scheme 884.Io9' Eight new enantioselective syntheses of 234 or its isomer have been reported since 1979. Four of them were initiated by chiral building blocks, and the others

20.

A

Acetals as Pheromones

C

B

AI-Hg

>

Sac!,

eq THF

C6H8 ( 50% lrm C )

(*).234

Scheme 881

>

MeCuCNU E$0,0.-78~C

6

MCPBA

, &o

1

OPO(OEt),

i

‘“‘QOH 2

(91% 1

1) MCPBA I CH,CI, 2) Cr0,.2C5H5NICHzC~ 3) Ph,P=CH,/THF ( 70% )

1) 0, / E$O

3)TsOH,Me,CO

(85.90% overall yield )

bOH’ OPqOEt),

MeCuCNU

(EO),POCI (ED%)

MeOH U / NH,

”%.

i

( 76% )

”””&

nhr

1) MeCuCNU / ECO

2) AcCI.C,H,N

/ CH,CI,

( &I% )

Jones CrO, ”“*,

2C,H5N>

CH,CI,

1

b0=bo 0

CrO,.

(70% from A ) (*) -234

Scheme 882

9 A

429

430

The Synthesis of Insect Pheromones, 1979-1989

__

( 98% )

( 95% )

1)

0

Ma2c+

[g!

M

U

3) 2) CrO,. LiAIH, 2C5H,N

cS%

MeN

~

N

~

S

.TsOH/C,H,

oHc*

( 0B% )

NaBH,CN

Hgl,.W

Ho

Ow0

aqTHF pH 2-3

aqTHF ( 95% )

B

+T* (+)-234

Scheme 883

9SlOO0C,40h 127%)

(f) - 234

employed chemical asymmetric reactions. Details of the onv rsion of D-glucose to 234 (Scheme 277a, Ref. I ) by Sum and Weiler appeared as a full paper.'096 Fraser-Reid et al. also employed D-glucose as their starting material and prepared 234 as shown in Scheme 885.'0y7.'098A compound (A)which is equivalent to the key-intermediate A of the Fraser-Reid synthesis was also prepared from D-galactose (Scheme 886). IoY9 Levoglucosenone, which is obtain-

20. Acetals as Pheromones

( 7)

gph3 1)H2/Pt02

OM8

EtOAc

(98%)

2) chromatog.sepn

+

BMe 9

OM8 :

431

1)Na/NH3 2) NaH / E t O PhCH,Br

1

able by acid-catalyzed pyrolysis of cellulose, was converted to (-)-&multistriatin by M. Mori et al. (Scheme 887).s251'i00A formal synthesis of the enantiomers of 8-multistriatin was reported by Mulzer et al. I l o ' Larchevgque and Henrot converted (S)-malic acid to 234 (Scheme 888), employing the stereoselective alkylation of hydroxylactone A to B.Ilo2 D-Glyceraldehyde acetonide was converted to a mixture of 234 and its @-,y-, and &isomers by means

432

The Synthesis of Insect Pheromones, 1979-1989

H, / Pd-C

I

A

2) Me,C(OMe),,PPTS CH2C12

f

'TsOH/C:Cl3

( 62% from A )

(S)-malicecid

3N-HCI MeCN.50°C (7%)

'

1) LiAIH, / EGO

(77% )

NaBH, I DMSO 50% (77=1

'

2)TsCI/C,H,N. ~ ~ a ~ i c H , c b

&

(lS,ZR,4S,5R)-(-)-134 [slop -45' ( hexam,

Scheme 888

20. Acetals as Pheromones

433

of vitamin B ,,-mediated electrochemical reaction to elongate the carbon chain (Scheme 889).36

1) H' I THF

v ( 87% from A ) 2) GLC sepn.

(lS,2R,4S,5R)-(-)-234 35

( 1 S,2S,4S,5R)-(-)-6

(1 S . ~ R , ~ R . ~ R ) - ( - ) - Y

56

(1 S,2S,4R,5R)-(-)-P

2

7

Scheme 889

A synthesis of (-)-6-multistriatin by Hoffmann and Helbig used the diastereoselective reaction between benzyloxyacetaldehyde A and the chiral boronate B, and yielded the product of 52% e.e. (Scheme 890)."03 Helbig converted

1)

&:='A lTHF

PhCH,OCH,CHO

A

Ph

6

2) N(CH,CH,OH),

, heal

,

P h C H , O ~

( 86% )

t

( 52

f6% e . e )

H O m

*

J

2N-HCI

'

heal ( 42% lrom C )

(lS.2S,4S,5R)-S-mulls~ialin

IuID20-46.6'

Scheme 890

( n-penlane )

Na Nr26% )

434

The Synthesis of Insect Pheromones, 1979-1989

83 ( I R,2S,4R,5S)-(t)-2M (aIDm,398' ( n-hexane 1

17

Scheme 891

epoxy alcohol A (Scheme 891), which was obtained by the Sharpless epoxidation, to (+)-234."04 Mori and Seu also employed the Sharpless asymmetric epoxidation for the synthesis of (-)-a-multistriatin 234 as shown in Scheme 892."05 By using the Sharpless asymmetric epoxidation, Chong and Wong prepared the key-intermediate C via B. '06

'

( 73%)

aq KOH

>

P h C H ~ O ~ 0 2 C ~ N oEIOH-THF z m.p. BPSS.S~C P~CH,O&~

NO2

(@=)

(ca.1Whe.e.)

1) H,/ Pd-C,NaHCO,/E(OH

o+

0 PhCH,O*

rSo&

(1 S,ZR,4S,5R)-234

lalons -46'

Nal,NaHC03/Me2C0

o+

2)TsCI/C5H5N ( 64% )

B

( nhexane )

Scheme 892

1) Me81 I penlane 2) TsOH / Me,CO ( 73% )

(94%)

C

20. Acetals as Pheromones

435

E. (1R,3S,5S)-1,8-Dimethyl-3-ethyl-2,9-dioxabicyclo[3.3.l]non-7-ene 235 ( C ,,H,,O,) and (lR,3S,5R)-1,8-Dirnethyl-3-ethyl-2,9dioxabicyclo[3.3,l]non-7-en-6-one236 (C I ,H1603) These are the male-produced pheromone components (together with 218) of the swift moth (Hepialus hecfa).'Io7Two independent but similar syntheses of 235 and 236 were published in 1986. De Shong et al. synthesized 236 via a furan precursor A (Scheme 893). I log The olefinic acetal235 was obtained in low yield

c:,

BF,*E$O (lR,3S,5R)-236 [a]o" +346.4'( CHCI, )

q q

t

1

;;g,

(tR,3S,5SJ-235

Scheme 893

by this De Shong protocol."08 Mori and Kisida synthesized both the enantiomers of 235 and 236 in enantiomerically pure state as shown in Scheme 894.959 By using the synthetic enantiomers, the absolute configuration of the natural pheromone was determined as (IR,3S,5S)-235 and (lR,3S,5R)-236 by GLC comparison of the synthetic and natural samples on a chiral stationary phase.959,

I109

F. 1,3-Dimethyl-2,9-dioxabicyclo[3.3.l]nonane(CgH1602) This is not a pheromone but a compound occurring specifically in the Norway spruce infested by the striped ambrosia beetle ( Trypodendron lineaturn).I I l o (The genuine pheromone of T. lineatum is lineatin 237.) However, a number of syntheses of this compound have been reported. Some authors stated 1,3dimethyl-2,9-dioxabicyclo[3.3. llnonane to be bioactive, when, actually, it is biologically inactive. Those who are interested in the syntheses of this bicyclic acetal are directed to Refs. 11 11-1 119.

436

The Synthesis of Insect Pheromones, 1979-1989

J ( -1000/.e.e)

(lS,3R,5S)-136 (aJoP.373°(CHCla)

(1S,3R,5R)-235 -1 lO"(CHCI,)

Scheme 894

G . (lR,4S,SR,7R)-Lineatin (3,3,7-Trimethyl-2,9dioxatricyclo[3.3.1 .04*']nonane) 237 (C l 602) This is the female-produced aggregation pheromone of the striped ambrosia beetle (Trypodendron linearum). Since 1979, six new syntheses of (f)-237 and four syntheses of optically active 237 have been reported. (1) Syntheses of (&)-Lineatin

In most cases, [2 + 2lcycloaddition reactions were employed to construct the cyclobutane ring. Borden et al. reported, without experimental details, four syntheses of (+)-237 (Schemes 895-898). 'I2' Cycloaddition of dichloroketene to olefins or photocycloaddition of vinyl acetate to a,P-unsaturated carbonyl compounds were the key-steps in these four syntheses. Weiler and his co-workers executed the photocycloaddition of allene to unsaturated lactone A to give a mixture of B and C. The mixture was further processed to finally produce a mixture of (f)-237 and its isomer, which were separable by chromatography (Scheme 899).Il2' [2 21Cycloaddition of acetylene to lactone A to yield B was the key-step of White's synthesis of (f)-237 (Scheme 900). ' I 2 * Smooth cycloaddition occurred only when A in acetonitrile saturated with a stream of

+

clw cfRTo-

CCI,

d

0 II

NaBH,

H

&OM-'

(kk237

Scheme 896

CO,G,H,N*HCI (k)-237

Scheme 897

>

HO

H

438

The Synthesis of Insect Pheromones, 1979-1989

2) MsCl I C,H,N A d

0

A d

3) KOBu' / DMC?

70

30

&237

Scheme 898

(k)-237 ( 23% )

(13.5%)

Scheme 899

acetylene was irradiated through Vycor glass. Tosylation of a mixture of C and D only resulted in the tosylate of C, leaving unreacted D, which was removable by chromatography. I 122 Two syntheses of (39-237 (Schemes 901 and 902) by Skattebdl were highly efficient by virture of the straightforward construction of the carbon skeleton by thermally induced intramolecular [2 21 cycloaddition (B + C)."23*1124 In the route shown in Scheme 901, the separation of C and D was troublesome,

+

20. Acetals as Pheromones

"'"7 LiNPt,/ THF

CH,CO,El (80%)

T H P 0 ~ C 0 2 E I

HO

439

1) AcCl (trace) EIOH 2) PPA.heal

B

m.p. 3&40°C

(i-Bu)#nlH

NaH

CH,C12 (85% 1

EbO ( 67% )

'

Scheme 900

B m.p.63.64"~

while in the other route (Scheme 902), cleavage of the epoxide D with periodic acid gave a separable mixture of E, F, and G, the latter two being the rearrangement products. The process shown in Scheme 902 was industrialized to produce (f)-237in 30%overall yield from A. [2 21 Cycloaddition of dichloroketene with a cyclic ally1 ether A was the

+

440

The Synthesis of Insect Pheromones, 1979-1989

A C H O

TsOH CnHn

+

>

>

S

C

H

O ( 92% )

A

I

D

C

i) (I-BU)#H I E$O 2) dil HCI ( 74% ) [ 30% overall l r m A I

(*I-237

Scheme 902

key step of the Oehlschlager synthesis (Scheme 903).'125 Dreiding and his co1) LWH,

CCl,COcl

2) PM-H,SO,

(83%)

A

4-5 days ( 6080% )

rnp ~ 7 - 9 8 ~ ~

(Ea%)

[ 10-i2% overall 1

Scheme 903

workers also employed the addition of dichloroketene in their synthesis of (f)-237(Scheme 904).'02 A lengthy route to (*)-237from a benzocyclobutene A was reported by Kametani et al. (Scheme 905),'05 which produced (*)-Be

(2) Syntheses of Optically Active Lineatin Five syntheses of optically active lineatin have been reported since 1979; four by resolution of intermediates and one starting from a sugar. The first step of

20. Acetals as Pheromones -0

441

1) Me,CO, 30% aq NaOH

Zn /ADOH

E&(PhCH,)NCI 2) Repeated

>

A

(f)-237

Scheme 904

+ Me0

OsO,-NaIO,

I-BuOH-THF-H,~ ( 73%)

'

2) DBU I CH ,,

( 69% )

(83%)

(see Scheme 634 )

A

I ) T60H / Me,CO

Ph,P

H

1) KBH(6-Bu), 2) T60H / Me,CO

c,

1) LiNP?,

'

3)Pd(OAc), / MeCN) ( 72% I

0 ( 87% )

( 69%

( 65% )

mp 72-7OoC

(f)-237

Scheme 905

442

The Synthesis of Insect Pheromones, 1979-1989

Mori-Sasaki synthesis was the photo-cycloaddition of A with vinyl acetate to give a mixture of B and C (Scheme 906)."26 The unwanted isomer B was

A

B

2

:

3

c U

E

(1R,4S,SR,7R)-237 [a]," +M"(n-penme) ( 82% 8.8.by Prof.Schurig's GLC analysis )

i _ j

F

(15,4R.65.75)-237 [a],22 40' (n-penbne) ( 74% 8.8. by GLC )

Scheme 906

destroyed by retro-aldol reaction in the course of the next conversion. Resolution of D as its carbamate diastereomers E and F was partially successful by chromatography to produce (+)-lineatin and its antipode of moderate e.e. In this work Mori misassigned the absolute configuration of the final products on the basis of misinterpretation of their ORDlCD data. Slessor and Oehlschlager et al. constructed the cyclobutane ring of 237 in a unique manner and resolved hydroxyacetal A via a mixture of carbamate diastereomers B and C (Scheme 907).' I 2 ' They were able to assign (lR,4S,SR,7R)-configuration to the bioactive (+)-237 on the basis of chromatographic and 'HNMR properties of B and C, as well as by comparing the chiroptical properties of 237 with those of other pheromone acetals. By the improved route as shown in Scheme 908, Mori et al. were able to secure the pure enantiomers of 237,and unambiguously establish

20. Acetals as Pheromones

443

AoMe1) UAIH,/ THF 2) TsOH CHCI,

(35%) (lR,4S,5A,7R)-237 B

no A

[alDZ456.3' (CHCI,)

(Oil)

2) HPLC 68p.

0

c

(oil)

2) TsOH CHCI, ( 47?4 )

(IS,4R,5S,IS)-Z37

[aIDn-71.6' (CHC13

Scheme 907

their absolute configuration as shown in the Scheme. 1 2 * * In this synthesis, (&)-lactone B was resolved by using derivative C of chrysanthemic acid as the resolving agent. The resulting diastereomers D and E were readily separable by MPLC, and the structure of D was determined by X-ray crystallographic analysis. The enantiomeric purity of (+)-237as well as that of its antipode were carefully estimated by GLC and NMR analyses."" Kandil and Slessor employed D-ribonolactone as the starting material and synthesized (+)-237,confirming its (lR,4S,SR,7R)-stereochemistry (Scheme 909). I3O This 16-step synthesis chemically established the absolute configuration of ( +)-237 and provided it in 2.7%overall yield.

'

444

The Synthesis of Insect Pheromones, 1979-1989

2)hactional dstilln

(86.5%)

0 ( 39% )

( +oJ+ )

( 56% from A )

B I

Removed from the lacrone by chromatog.

( 86% )

1

Scheme 908

21. SPIROACETALS AS PHEROMONES Since 1977 many spiroacetals have been isolated and identified as insect pheromones or secretions, mainly by W . Francke and his co-workers. Among them 1,7-dioxaspiro[5.5]undecanes exist not only as insect pheromones but also as antibiotics such as avermectins and milbemycins. Synthetic chemistry of 1,7dioxaspiro[5.5]undecaneswas reviewed by Kluge. ' I 3 ' A comprehensive review of the chemistry of spiroacetals appeared in 1989.'13' 'Hand I3C-NMR spectra of spiroacetals were measured and analyzed. I 133*I '34 Mass spectra of alkyl- 1,6dioxaspiro[4.5]decanes were discussed by Francke et al. I 135 Stereoelectronic

E

21. Spiroacetals as Pheromones

u,&

AcO OAc OH

0 l ) ~ ~ I / E ~ O

Ho OH (65%) D-Ribondaclone

HO OH

K

x

2) A%O I C,HSN ( 56% )

OHCJ

OSEM

(95%)

445

( ffl% )

OX0 mp 125-126°C

~

$

~

?~

NaH I THF

OX0

1) SEMCI.(i-Pr),NEl I THF

2) NaOH aq I M O H

(Q W

1

E

'

)

Me0 z

>

NC

OMe

d b

K

SEMI Me3SiCH2CH2-

Scheme 909

effects in spiroacetals (especially 1,7-dioxaspiro[5.5]undecanes) were studied by Deslongchamps et al. to deduce the stable conformers (Scheme 910)."36

most sLable

( Okcal I mot )

( 2.4kcal/m d )

Scheme 910

( 4.6kcal I m d )

446

The Synthesis of Insect Pheromones, 1979-1989

A. Chalcogran (2-Ethyl-1,6-dioxaspiro[4.4]nonane)238 (C,H ,602) This is the major component of the aggregation pheromone of the six-spined spruce bark beetle (Pityogenes chalcographus), as first discovered by Francke et al. in 1979."37Another component of the pheromone is methyl (2E,42)-2,4decadienoate 145. There are four stereoisomers of chalcogran 238 (Scheme 91 1). Hindguts of the male beetle contain the most active (2S,5R)-238and least

Scheme 911

active (2S,5S)-238.' 1 3 7 Two unnatural isomers, (2R,5R)-238 and (2R,5S)-238, had intermediate activities."37 A mixture of 145 and 238 is marketed as a trap lure for P . chalcographus. I 1 3 7

( I ) Syntheses of a Stereoisomeric Mixture of Chalcogran There are several reports on the synthesis of a mixture of all of the isomers of 238. Francke and Reith prepared an isomeric mixture of 238 (Scheme 912),

238

Scheme 912

starting from furfural and butanone. ' I 3 ' Other alkyl- 1,6-dioxaspir0[4.4]nonanes were also synthesized and their mass spectra discussed."38 Smith and his co-

21. Spiroacetals as Pheromones

447

workers started from (&)-4-hexanolideand prepared 238 in 37% or 63 % overall yield (Scheme 913).1'39*"40 Torgov's synthesis of 238 (Scheme 914) is a mod-

138 ( 37% overall yield )

238

( 63% overall yield )

Scheme 913

238

( 5 4 % lrm E )

Scheme 914

ification of the Francke synthesis (Scheme 912), producing 238 in 51% yield from the furan compound Ireland and Habich employed the hetero-DielsAlder reaction between furanoid exocyclic vinyl ether A with acrolein to give B, which was converted to 238 (Scheme 915)."42."43

Ph,PCH,.I THF

(re%)

H, I Rermy-Ni

THF (89%)

Scheme 915

238

448

The Synthesis of Insect Pheromones, 1979-1989

Nitromethane, ethyl vinyl ketone, and acrolein were the starting materials in Rosini's synthesis of 238 (Scheme 916). Reissig and his co-workers em-

G

C

H

O

NO2

@&

OH

> -(85%)

NO2

(65%)

238

Scheme 916

ployed nitropropane for the synthesis of 238 (Scheme 917). 'I4' The key-step of

Scheme 917

Ley's synthesis of 238 was the cyclization of hemiacetal A with N-phenylselenophthalimide and zinc bromide to create B (Scheme 918)."46 1,7-Nonane-

0 ZnBr2(0.1eq)I CH2CI, (45%)

'

Raney - Ni c ? o y s $ P h B

;vJ)

238

Scheme 918

diol was converted to 238 by alkoxy radical process with either lead tetraacetate or silver oxide-bromine (Scheme 919).' 147

21. Spiroacetals as Pheromones

449

(48%)

Scheme 919

(2) Syntheses of Optically Active Chalcogran Schurig's complexation GC method can be used for the estimation of the enantiomeric excess of the enantiomeric pairs (cf. Scheme 91 1) of chalcogran by using an optically active nickel complex as the stationary phase. I 14' Starting from D-glucose, Redlich synthesized (2R,5RS)-238 and (2S,5RS)-238 as shown in Scheme 920. I '49*I 150 (2R,SRS)-Chalcogran 238 was also synthesized by Seebach and his co-workers, by employing (S)-malic acid (Scheme 921). Enders used acetone dimethylhydrazone and epoxides as starting materials to prepare (2S,5RS)-238 (Scheme 922).Il5* In a recent synthesis by Hogberg et al., all the stereoisomers of 238 were secured for bioassay purpose."53 As shown in Scheme 923, their synthesis was a modification of Smith's route (Scheme 913). Their starting materials were the enantiomers of 4-hexanolide A, which were prepared by chromatographic resolution of (*)-A. (2R,SRS)-Chalcogran could be separated by careful chromatography on silica gel to produce (2R,5R)-238 and (2R,5S)-238. Similarly, (2S,SS)-238 and (2S,5R)-238 were also prepared. Their purities were estimated by capillary GLC analysis on a chiral stationary phase, Ni(I1) bis(3-heptafluorobutyryl-1-(R)-camphorate,in SE-54 (Scheme 923).

B. 1,7-Diethyl-1,6-dioxaspiro[4.4]nonane 239 (C, IH2002)and 1,7-Dipropyl-1,6-dioxaspiro[4.4]nonane240 (C 3H2402)

,

These are the components of the pheromone bouquets of Andrena bees. The palaearctic bee (Andrena wilkella) produces 239, 154 and A . haemorrhoa produces 240."55 Enders prepared 239 and 240 both as a stereoisomeric mixture, by alkylating acetone dimethylhydrazone with epoxides (Scheme 924). I ' 5 2

450

"'b0 - Hobo

The Synthesis of Insect Pheromones, 1979-1989

c-Glumse

k"ow">

1) NaH,CS*Mel/THF

known

2) (n-Bu),SnH.AIEN I tduerm 3) 3%HCI / MeOH

"t

n

TiTHp ' Y

n-BuLl/THF

"t

A

1) CollkJine*HCI ;HgO/ aqMeOH

B r v O T H P

Et

Et

n A

HS(CHJ,SH.BF,*E(,O

/ CHCI,

- kOH(913:2)

n

OH

I)Me,CO.CuSO,,H,SO 2)TsCI / C,H,N B)LIAIH,

OH

n-BuLi) THF

%

PhCO,H,Ph,P EIOzCN-NCO,Et THF

(2S.55) -238

(2S.5R). 238 (13)

Scheme 920

'

'

21. Spiroacetals as Pheromones

451

(S) - Malii acid

0 svs

l)n-BUti/THF 2)BfV\OEE (84%)

'

As

s

~

n

n - E!uLi/MF

O

E

E A

OEE

H

(93%)

A l)Me2CuLi / THF 2 ~ iHCI 1 I THF (74%)

>

OH

HgCI eo%&OH

>

(477")

(2R,5R). 238

(2R,5S). 238 1: 1

[abn +13.5'(CDCI,) Scheme 921

C. 2-Methyl-l,6-dioxaspiro[4.5]decane241 (C,H I602) This is a pheromone component of the common wasp (Puruvespulu vulgaris). The absolute configuration of the natural product is still unknown. (1) Syntheses of a Stereoisomeric Mixture of 241

Several syntheses of a stereoisomeric mixture of 241 were reported by the same methods as those used for the synthesis of 238. Starting from (+)-4-pentanolide, Smith and his co-workers synthesized (34-241(Scheme 925)."39 Ireland's hetero-Diels-Alder route was used to synthesize B from A (Scheme 926), and

452

The Synthesis of Insect Pheromones, 1979-1989

238

SiO, chromalog.

sew

'

-

and

(2R,5R)-238

[ a~ ~ ~ & d ' ( h e x a n e ) (95.3% pure)

(2R,5S) 238

[ a]D"tQ8f40(hexsne) (91.3%pure)

Scheme 923

239

240

Scheme 924

21. Spiroacetals as Pheromones

453

(21% overall yield)

Scheme 925

Scheme 926

B can be a precursor to 241.'14* Ley's organoselenium-mediated cyclization was applied to the synthesis of 241 (Scheme 927).'146*"57 In Rosini's synthesis

d N S e P h

0 ZnBr, I CH,CI, (78%)

'

a

SePh

Raney-Ni,

€OH (90%)

241

Scheme 927

of 241, 2-nitrocyclopentanone was used as the starting material (Scheme 928).1'58Utimoto prepared 241 in a simple manner by a regioselective acetalization of acetylene diol A (Scheme 929). I 159

241

Scheme 928

A

240

Scheme 929

454

The Synthesis of Insect Pheromones, 1979-1989

(2) Syntheses of Optically Active 241 The first synthesis of (2S,5RS)-241was reported by Schurig and his co-workers starting from ethyl @)-lactate A (Scheme 93O).lt6OThe enantiomeric purity of

(25.55). 241

(2S,5R). 241

Scheme 930

the product could be checked by GLC on manganese-bis-3-heptafluorobutyryl(R)-camphorate. Seebach et al. synthesized (2R,5RS)-241starting from (S)malic acid (Scheme 931). Ley's synthesis of (2R,5RS)-241was achieved by 1)n- BULI/THF

s,

CI-OEE

OEE

n >

n

_____)

-0EE

(81%)

l)UEEt,H / THF 2) NaOH - H202 3)dil HCI / THF (78%)

.

n b L l / THF

>s fs i

O +H OH

HGI,

90% MeOH

(50%)

Scheme 931

>

'+*a H

(2R,SRS). 241

[a],"

+13.Q0 (CDCI,)

alkylation of 2-benzenensulfonyltetrahydropyranA with chiral iodide B (Scheme 932). 1161, 1162 1)n - BUU I THF OTHP

[ aID"- 12.1' [ a 1,". 21.1'

Scheme 932

(ref.1161) (ret.1162)

21. Spiroacetals as Pheromones

455

Stereocontrol of the chirality at the spirocenter of 241 was achieved by Iwata et al. by intramolecular Michael addition of the hydroxy group to the a,@unsaturated sulfoxide moiety of A to produce B (Scheme 933), yielding dias-

1) KH / THF

B

(2$*,5S*).241

Scheme 933

tereomencally pure (2S,*5S*)-241 and ( 2 S * , 5 R *)-241."63 Iwata further improved this strategy to synthesize all of the four stereoisomers of 241 (Scheme 934). Three steps in Scheme 934 are noteworthy: (i) stereoselective reduction of A to create either B or C as the major product by changing the reducing agent; (ii) kinetically controled cyclization of B and C to produce D and E, respectively; and (iii) conversion of D and E to thermodynamically more stable F and G by acid treatment. D. 7-Methyl-1,6-dioxaspiro[4.5]decane242 (C,H 1602) Together with 241, this is a pheromone component of the common wasp (Puravespulu vulgaris). The absolute configuration of the natural product isolated from an American bark beetle (Conophthorus sp.) was shown to be (5S,7S)-242. I 166 (1) Syntheses of (+)-242

Francke et al. prepared (*)-242 starting from y-butyrolactone and 6-caprolactone (Scheme 935)."33 Only a single diastereomer was obtained due to the

456

The Synthesis of Insect Pheromones, 1979-1989 1) A020 / CaHaN

PCC

2) TsOH / MeOH

3) TsOH / C,H,

OH

4)

$C03 I a q W H

P

(66.5%)

O

(91.4%)

C (76%)

D

-

E

TsOH MeOH

Q

F

TsOH

W H '

Q

0

Scheme 934

1) NaOEl I EIOH

0

0

2) dil HCI (

f ).

Scheme 935

.

NaOAc'

242

H

(66.9%) CH2C12

21. Spiroacetals as Pheromones

457

oxygen anomeric effect."33 Smith et al. also started from y-butyrolactone (Scheme 935, lower line). Koiluk et al. started from 6-methyldihydropyran and employed a photochemical reaction for spiroacetal formation (Scheme 936). I Ley used organoselenium-mediated cyclization to prepare (*)-242 H

O

~

TsOH/THF (72%)

'

O

H

D

O

V

O

H

* (75%)

1) hv 1 C6H8 2) Ac,O / C,H,N

O o - C H O

3) SiO,

chromalog. sepn

(Scheme 937). I '46v I 157 Ley's other method was the Horner-Wittig reaction

0

ZnBr, I CH,CI, (81%)

SePh

EtOH (e8X)

> (*)-242

Scheme 937

of 2-diphenylphosphinoxytetrahydropyran with y-valerolactol (Scheme 938). I 169 Functionalized nitroalkanes were the intermediates in Rosini's

(

f ) -242

Scheme 938

458

The Synthesis of Insect Pheromones, 1979-1989

synthesis of (*)-242 (Scheme 939)."5s The alkoxy radical route was also successful in providing (+)-242 (Scheme 940)."47 NsNO,

7 = (87%)

cuo

OH (85%)

l)N,aOH/ E t o g 2)dil H2S0, (74%)

@ (k).242

Scheme 939

Scheme 940

(2) Syntheses of (SS,7S)-242 Schurig and his co-workers synthesized (5S,7S)-242 from ethyl (S)-lactate A (Scheme 941).II6OIn this paper, complexation GLC analysis of 242 is discussed

A

0

0

(SS.7S)- 242

0

B

0

)LCO,E!

0 2)H'

Scheme 941

in detail. The key-step of the Schurig synthesis was the alkylation of the dianion, which was derived from a-acetyl-y-butyrolactone as developed by Mori et a ~ " ~Smith ' and his co-workers converted (S)-propylene oxide into (5S,7S)-242 (Scheme 942). 'I4'

21. Spiroacetals as Pheromones

459

Scheme 942

E. 7-Ethyl-2-methyl-l,6-dioxaspiro[4.5]decane 243 (CI IH2,02) The two diastereomers of 243 were first found in the workers of P . vulgaris, and serve as the constituents of their anti-aggregation pheromones. 1 7 ' These diastereomers were also found in the volatile secretion from the mandibular glands of the bee pollinator, Andrena haemorrhoa.'i72An isomeric mixture of 243 was synthesized by Smith and his co-workers (Scheme 943) starting from

'

1) H, IRh .Al,O, lMeOH

(56% overall)

(f)-243

Scheme 943

(f)d-pentanolide. I I4O All of the four energetically possible stereoisomers of

243 were synthesized by Mori and Ikunaka by employing dianion alkylation as

the key-step (Scheme 944). The starting chiral building blocks were ethyl (Qlactate, dimethyl @)-malate, and methyl (R)-3-hydroxypentanoate.Lactone B, which was prepared from propylene oxide A, was connected with C to produce D, which finally yielded 243. By changing the partner of the connection, all of the four thermodynamically stable isomers of 243 were synthesized.' 173

F. 2-Ethyl-7-methyl-1,6-dioxaspiro[4.5]decane244 (C IHZ0O2) This is a pheromone component of P . ~ u l g a r i s " ~and ' Andrena haemorrhoa. The parasitoid wasp (Megarhyssa nortoni nortoni)' 174 and the cucumber fly (Dacus cucumis)' '75-I 17' also produce 244. An isomeric mixture of 244 was prepared by Smith and his co-workers as shown in Scheme 945.

'

460

The Synthesis of Insect Pheromones, 1979-1989

penlanoale

&I HCI (6746frarnD ]

-

-

(2R.5R.7R) 243 [a]D24 +78.4' (penlane)

(R)-E+(S)-C

7-

( 2RS.7.S ) - 243

I a 1020-97S0 (penlane)

T

(S)-S+(R)-C

(S)-E+(S)- C

( 2S,5R,7R) .243

(25,55.75)

I a lon

a)oP+i~ (penlane) ~O

Scheme 944

l)HZ/Rh-A120,/MeOH

O T ~ P2) dil HCI

(52% overall)

Scheme 945

- 243

-76.i' (penlane)

21. Spiroacetals as Pheromones

461

G. 2,7-Dirnethyl-1,6-dioxaspiro[4.6]undecane245 (CI IH2002) This is a component of the volatile secretion from the mandibular glands of A . haemorrhoa.”55Mori et al. synthesized four thermodynamically stable isomers of 245 in a manner similar to that used for the synthesis of 243 (Scheme 946).’17’

bulewale

1)UAIH 2)TsCIfC,H,N> (9 %)

(73%)

OTHP

Nal .NaHCO,

/Ic\pTs Me,CO (92%)

>

W -A

TsOH , MgSO,

EbO

171%)

(2S,5S,7R) .245 +97.2’ (penlane)

(S) - A +(R) - B

I

(S). A + (S) - B

( ZR,5R,7S). 245

lab2’.96.0’ (penlane)

Scheme 946

Alkylation of B”73with A gave C, which was hydrolyzed and decarboxylated. In this case, keto diol D could be isolated due to the unfavorable nature of the cyclization leading to a seven-membered ring. Under the forcing condition that employs magnesium sulfate as the dehydrating agent, D yielded 245. In this paper, [a],values as well as the I3C NMR data of various spiroacetals are compared and discussed. I 17’

The Synthesis of Insect Pheromones, 1979-1989

462

H. 1,7-Dioxaspiro[5.5]undecane 246 (C9HI6O2),3-Hydroxy-1,7dioxaspir0[5S]undecane 247 (C,H,,O,), and 4-Hydroxy-l,7dioxaspiro[5S]undecane 248 (C9H1603) The major component of the sex pheromone produced by the female olive fruit fly (Dams oleae) was shown to be 1,7-dioxaspiro[5.5]undecane (olean) 246 by Baker, Francke, and their co-workers in 1980."789I 179 Two hydroxyspiroacetals 247 and 248 are the minor components of the pheromone."79*"80In the field test, (*)-246 was proved to be active."78'"79'"8'

( I ) Syntheses of the Racemates of 246, 247, and 248

'

Baker et al. synthesized (+)-246 from 6-valerolactone (Scheme 947). *'71

I 179

If)-246

1

I-"'"'

Scheme 947

The Homer-Wittig reaction of aldehyde B with 2-diphenylphosphinoxytetrahydropyran A was the key-step in Ley's synthesis of (*)-246 (Scheme I 948). Ousset et al. also employed the Wittig reaction to prepare (+)-246

(62% from A)

(93%)

(f)-246 Scheme 948

(Scheme 949).468Ley's second synthesis of (f)-246 was based on the alkylation of 2-benzenesulfonyltetrahydropyran (Scheme 950);' I 6 l . I 16* (+)-248 was also synthesized by the same method (Scheme 950). 1 6 ' A unique synthesis of (+)-246 by Brinker et al. was achieved by a carbene insertion reaction (Scheme 951).1'82In this synthesis, however, two byproducts were also obtained. Reddy

'

21. Spiroacetals as Pheromones

6

Ph,P,HEr CH,CI, (85%)

oPPh3Ei 1 ) n -EuLi/THF -HMPA 2)OHC(CH2),0THP

(@JW

(f)4 4 6

463

SiO, /CH,CI,

>

Scheme 949 1) n .EuU AHF

Br -0THP

2)CSA

PhSO,H,CaCI,

(71%)

(f) -246

(7W

O Y PhO

(f) 448

2) dil HCI NeOH

(4W

Scheme 950

"H (+)-246

0

36:38:26

Scheme 951

-a

and Mitra prepared (f)-246by bis-alkylation of acetone dimethylhydrazone (Scheme 952).470The key-step in DeShong's synthesis of (+)-246and (&)-247 1) n - EuLi

-LOTHp On-EuLiI THF

*) B r v O T H P 31 dl HCI (65% overall)

2, E ~ ~ O T H P

Scheme 952

(k) -246

464

The Synthesis of Insect Pheromones, 1979-1989

was MCPBA oxidation of furan A to produce pyranone C via B (Scheme 953).'183 Kocieriski synthesized ( f )-246 by alkylidenation of ester carbonyl

145 : 1

Scheme 953

with a metal carbene complex (Scheme 954).

Brimble et al. prepared (+)-246

(62%)

THPO

(f)-246

Scheme 954

from phenylsulfone A and 6-valerolactone (Scheme 955). I 185 Baker's synthesis c _ nL

1) 2eq.n-BuLlI THF

3)6at.NaH2P04 aq

Scheme 955

of hydroxyspiroacetals (f)-247and (f)-248(Scheme 956) was achieved by hydration or hydroboration-oxidation of unsaturated spiroacetals A or B.' 1793I I8O

21. Spiroacetals as Pheromones Ambertile IR-118 (H')

465

-.n

Scheme 956

Kocieriski and Yeates synthesized (f)-248,employing the organocuprate derived from 6-lithio-3,4-dihydro-2(H)-pyran(Scheme 957). 'Ix6 A cation-olefin

1) HCI - H,O

HO

2) SO2chrmatog. (64% overall) 3)Reuysl'n

HO

(f)-248

m.p. 4 8 . 4 9 ' ~

Scheme 957

cyclization reaction was used by Kay and Williams to prepare (+)-248(Scheme 958)."*'

(61%)

(*)-zqe

Scheme 958

The Synthesis of Insect Pheromones, 1979-1989

466

CUCC, cuo

(75%)

Me,CO-H,O (r05%)

3 days

OH

35

(4R,8R)- 248

:

65

[u]~"-58.3°(CDCl.J

1) A1203/ EbO, 4h 2) H 2 / Pd. C, El,N / E$O

(ORBS).C

('O0/.)

SiO, chromatog.

+

(4R,6S) . A

TsCI I C,H,N

(4R,BS)- A

& &

'

sepn.

Scheme 959

1) UAIH,/ Eb0

n&Li I THF

2) TsCl I C,H,N

-2

3) Nal, NaHCO, Ne,CO' (70%)

I X

(60%)

n&Li

(Me,N),POCI THF/TMEDA

HO

(4S,~S.lOS)~ a A

,

(81%)

m.p. 153- 154OC

(Me,N),PO

.f& WNMe,),

6

(55%)

U/EtNHZ I. BuOH. THF

(73%)

(S) .248

+ t09,3~(n-pentane)

PCC / CH,CI,

0 C

(4R.BS.lOR). D

(4R,6R,lOR). B m.p. 150. l s t 0 c

Scheme 960

( R ) .246 (u]:' -121.Bo(n-penme)

21. Spiroacetals as Pheromones

467

(2) Syntheses of the Enantiomers of 246, 247, and 248 Four different syntheses of the enantiomers of 1,7-dioxaspiro[5.5]undecane246 have been reported. Redlich and Francke began with D-glucose and prepared both the enantiomers of 246 and (4R,6R)-248 (Scheme 959).'188 Mori's first synthesis (Scheme 960) used two molecules of (S)-malic acid to construct a molecule of 246.'Ia9. Deprotection of A yielded (4S,6S,IOS)-B with two equatorial hydroxy groups. This was oxidized to C, the reduction of which with L-selectride@ produced diaxial diol D. When D was treated with acid, it isomerized to (4R,6R,10R)-B with two equatorial hydroxy groups. Thus, the hydroxy groups were used as the handle to fix the conformation of spiroacetals. 19' In Mori's second synthesis, only one molecule of (S)-malic acid was incorporated into 246 (Scheme 961)."89."91 Conversion of (4S,6S)-248 to (4R,6R)-248

(4S,6R). B

A

Scheme 961

The Synthesis OF Insect Pheromones, 1979-1989

468

via C and (4R,6S)-B was the key transformation in this synthesis. The enantiomeric purity of (R)-246 and (S)-246 was determined by complexation GLC.'19' Iwata et al. synthesized both (R)-246 and (S)-246 starting from (-)menthyl (S)-p-toluenesulfinate (Scheme 962).I 19** I 193 The key-step of their syn-

0

.

Raney Ni

iJ

MeOH (78%)

Raney - Ni

C

(83%)

(S)- 246

thesis was the diastereoselective intramolecular Michael addition of the hydroxy group of A, which provided spiroacetal B as the kinetically controlled product with the axial sulfinyl group. Treatment of B with acid effected its isomerization to the stabler isomer C. Desulfurization of B and C produced (R)-246 and (S)-246, respectively. Both the enantiomers of 3-hydroxy- I ,7-dioxaspiro[5.5]undecane 247 were synthesized by Mori et al., starting from (S)-malic acid (Scheme 963).'t9'* In this particular case, deprotection of A yielded all of the four possible isomers of the spiroacetals, (3S,6S)-247, B, C, and D. Another noteworthy finding was the stabler nature of the axially substituted spiroacetal E in comparison with its

-

21. Spiroacetals as Pheromones

HO

1 ) TsCl I C,H,N 2) Ub, NaHC0,I DMF

known

" G

.

(S) Malic acid

A

+

R

.

469

THF

(88%)

& + (2S.S) (1 5%)

~

c

1)TsCI / C,H,N (13%)

DNBO

F

29

Scheme 963

isomer F with an equatorial substituent. Both (2R,SS)-241 and (2R,SR)-241 were also obtained by derivation from C and D, respectively. Bestmann and Schmidt synthesized (3S,6S)-247 starting from D-glyceraldehyde acetoThey executed the cyclization of the same keto trio1 as previously nide. reported by Mori et al."9i As shown in Scheme 964, Bestmann also obtained a mixture of all of four possible spiroacetals, one of which was (3S,6S)-247. However, the exact ratio of the products was not reported.

470

The Synthesis of Insect Pheromones, 1979-1989

+

(2S.55) .c

(2S.5R). D

&

OH

+

(3S,6R) - B

&JOH

(3S.6S). 247 m.p. 95 - 9 7 ' ~

[ale" +90.5°(CH2C12)

Scheme 964

Both the enantiomers of spirobi-l,4-dioxane A were prepared from D-frUCtose (Scheme 965), although their bioactivity was not studied. I 1969'I9' Hani-

Scheme 965

otakis et al. synthesized (f)-1,5,7-trioxaspir0[5.5]undecane B (Scheme 965), and found it to be highly bioactive against the olive fruit fly (Dacus oleae)."98 It must be mentioned that (R)-246 was active on the male D. oleae, while (S)-246 was active on females."99 The natural pheromone produced by the female D. oleae is (f)-246."99 An Australian fruit fly, D. cacuminatus, also produces ( f1-246. I 175

I. (2S,6R,8S)-2,8-Dimethyl-l,7-dioxaspiro[5.5]undecane 249 (C I IH2002)

2,g-Dimethyl- 1,7-dioxaspiro[5.5]undecane 249 can exist as three diastereomenc pairs (total six) of the enantiomers (Scheme 966).1133 The (2S*,6R*,8S*)-

21. Spiroacetals as Pheromones

-

(2S,6R,BS) 249

-

(2S,6S,ES) 249

zz

EE most stable

unstable

471

-

(2S,6S,BR) 249

EZ slable

Scheme 966

isomer of 249 is the major component of the cephalic secretion of Andrena ilke el la."^^ In this bee secretion, a small amount of (2S*,6S*,8R*)-249 was also present. Tengo et al. showed (2S,6R,8S)-249 to be the bioactive isomer in attracting patroling male bees in the field.'2oo The (2R,6S,8R)-isomer was behaviorally inactive, and in a racemic mixture it did not inhibit the response of the bees. The diastereomers of 249 other than the (2S,6R,8S)-isomer were almost inactive. The (2S,6R,8S)-isomer was later identified as the major component of the rectal gland secretion of the male cucumber fly (Dacus cucumis) and D. h~lfordiae."'~*~'~~ In the former fly, the (2S*,6S*,8S*)- and (2S*,6S*,8R*)-isomers were also found as the minor components of the secretion. 17', The parasitoid wasp (Megarhyssa nortoni nortoni) also secretes 249. ( 2 s *,6R *,8S *)-2,8-Dimethyl-1,7-dioxaspiro[5.5]undecane ( f )-249 was first synthesized by Francke et al. starting from 5-hexanolide (Scheme 966). Its (2S*,6S*,8R*)-isomer was also characterized, and the NMR spectra of both the isomers were analyzed. '33 Kitching et al. was able to characterize all three isomers, (2s*,6R *, 8s* )-, (2s*,6S * ,8R * )-, and (2R* ,6R * ,8R *)-249, by synthesizing them from dienone A via mercury(I1)-catalyzed cyclization reaction (Scheme 967). l Z oTheir ' 400 MHz 'H-NMR spectra were also recorded. The noteworthy feature of this synthesis was the isolation of even the least stable (2R *,6R*,8R*)-isomer, which readily isomerized with acid to the stablest (2S*,6R*,8S*)-249.1176 Giese's synthesis of a mixture of (2S*,6R*,8S*)-249 and (2S* ,6S*,8R*)-249 was based on the radical carboncarbon bond formation (Scheme 968).

'

'

'

472

The Synthesis of Insect Pheromones, 1979-1989 +

-Mew

+

HCO~EI 1)EbO

Hg(OAo)zlTHF-HzO

0

ismin

2)KOH

( Hw ) HgCl

A

4

ClHg

ClHg

ClHg

D

C

l)NaBH, NaOH 2)Sepn by pep GLC

'

I (2S'.6R',OS*). 249

(2S'.6S'.8d)

40

- 249

40

B

'%

HgCl

.

E

(ZR',Sd.BR')

- 249

3

Scheme 967

(6% Irm propem)

(2S*,6R1,8S*).249 1

(9596)

(2S*.6S*.ER*)~249 1

Scheme 968

Mori and Tanida synthesized both (2S,6R,8S)-249 and its antipode, starting from ethyl acetoacetate A (Scheme 969). '202*'203 Reduction of A with baker's yeast produced (S)-B, which was converted to (2S,6R,8S)-249 via (S)-C. On the other hand, (R)-D was prepared from (S)-B via Mitsunobu inversion and converted to (2R,6S,8R)-249. This 1981 synthesis was later improved by Mori and Watanabe. I2O4 By using the pure enantiomers of ethyl 3-hydroxybutanoate as the chiral building blocks, they secured pure (2S,6R,8S)-249 and (2R,6S,8R)-249 (Scheme 970). I2O4 Moreover, they clarified how it was possible to prepare (2S,6R,8S)-249 of 98.7 % e.e. starting from ethyl (S)-3-hydroxybutanoate of 8 5 % e.e. (Scheme 970).12" Employing (S)-malic acid as one of the starting materials, (2R,6S,8R)-249 and (2R,6R,8S)-249 were synthesized by Mori and Watanabe (Scheme 971).I2O4In this synthesis, the enantiomeric

21. Spiroacetals as Pheromones

0 /LCCO,Me

NaH,n-&IU/THF

-

(S) c (75%)

OTHP

473

1) KOH I MeOHa

0 (89%)

(2S.6A.S)- 249

C0,Me

2) TsOH / MeOH

(30%)

(2R,6S,8R). 249

[alpn -51.6°(penlme)

[a)," +51.?(penlane) (4 as.) %

( 4 6 % e.e.1

Scheme 969

purity of C could be determined by the 'H-NMR analysis of its MTPA ester. It should be noted that E could be isomerized to D because the 3,5-dinitrobenzoate of D was crystalline, while that of E was an oil. Thus 3,5-dinitrobenzoate of E was isomerized with acid, and the crystalline 3,5-dinitrobenzoate of D could be separated. Isaksson et al. reported the preparative separation of the enantiomers of (2R*,6S*,8R*)-249 and (2R*,6R*,8S*)-249 by chromatography on microcrystalline triacetylcellulose. 1205 With this technique, they could prepare all four energetically stable isomers of 249.

J. 2-Ethyl-8-methyl-1,7-dioxaspiro[5.5]undecane250 (C 2H2202) This is the unusual even-carbon-membered spiroacetal found in the rectal gland secretion of an Australian fruit fly (Ducus occipitulis).1175 Kitching et al. synthesized (2R,4S,8R)-250 by means of organotin chemistry coupled with oxymercuration-cyclization (Scheme 972).5'2 This spiroacetal was also found in the oriental fruit fly (D. dorsulis) and D. lutifrons.1175

The Synthesis of Insect Pheromones, 1979-1989

474

25.5% over

-

(R) - A --100%e.e. from PHB

(2R,6S,8R) 249

[a]:' +57.6'(pentane) (-100% e.e.)

-

(2S,6R,8S) 249

[a]:'

(2S,6R,BS) - 249 0.925 X 0.925 ii

152

-

(2R.6S.8R) 249

-

-

1

(2S.6S.8R) 249

: 0.075 X 0.075

0.925 X 0.075

1

1

-56.O0(penIane)

(2R,6R,8S) 249

:

0.075 X 0.925 1

13.9

88.1

The diaslereorners were separable by SiO, chromatography. 92.5'- 7.5' Enantiomeric purity of (2S,6R,8S) 249 = x 100 = 98.7% 92.5' + 7.5'

-

Scheme 970

21. Spiroacetals as Pheromones

475

A

(66%)

roH

E

Scheme 971

>?

l)Ha(OAo),/ l%aqHCIO,-THF(l:l)

.

2) NaQH, NaOH / CH&I, PhCH,NEt$I (70%)

- H,O

(2R'.4S,8R')-2W

Scheme 972

K. 2-Butyl-8-methyl-l,7-dioxaspiro[5.5]undecane251 (C ,4H2602) This unusual even-carbon membered spiroacetal was found as a minor component of the rectal gland secretion of the fruit fly species (D.larifrons) found in Southeast Asia and Hawaii."75 O'Shea and Kitching synthesized 251 by the oxymercuration-cyclization route (Scheme 973).5

476

-

The Synthesis of Insect Pheromones, 1979-1989

1) Hp(OAc)Z/aq THF NaOH aq, PhCH,NEt,CI CH,=CHCN / CH,CI, NaEH,

,

2) DHP, PPTS/ EbO

1) Hg(OAc),/ dl HCIO,

.

OH

OTHP

0

(W%)

W0-.60%)

>A

- THF

2) NaOH NaBH,

(@w

251

Scheme 973

L. 2,8-Dimethyl-1,7-dioxaspiro[5.5]undecan-4-01252 (C IH2003) This is a minor component of the mandibular gland secretion of Andrena wilkellu.'"* The absolute configuration of the natural product has not yet been determined. Both (2R,4S,6S,8R)-252 and its antipode were synthesized starting from chiral building blocks of carbohydrate origin by Redlich and Schneider (Scheme 974).I2O6Coupling of the building blocks A with Bi207yielded the enantiomers of 252. This synthesis is selective, but lengthy.

yo dcHO H

S

~

(28%)

1) I-EuCOCI / CH ,N ,

21 DHP. TsOH Idiom% (86%)

S

a 431 I ) TsCl / C H N

H

-

1) n.BuU / THF

OH

(65%)

0 11 OMP 1 ) N a O M e l W H 1 . 6 u C O d 21 Ph"P. Irnldazole'

(3S.5R). B

Scheme 974

2 Hod

~ ) R ~ I W ~ - N IH/ E

OH

:THP

OH

21. Spiroacetals as Pheromones

477

1) Ph,P. PhC02H

2) NaOMe / MeOH

s-

+ (R)-A

B

(3S.5R) -

-

o x 0

(3R.5S) - E

2) HgO, CdlidinwHCI) MeOH 3) Ac,O IC,H,N, chmmalog. (75%)

(89%)

(2R,4S,6S,BR)

MeOH (81%) (ZR.45.6S.8R) - 252

[aloP+74.5°(penme) *S

n

+ (*)-A

(3R.5S) - B

(2S.4R.6R.BS) - 252

[alDa-75.o0(penlane)

Scheme 974 (Continued)

M. 2-Methyl-l,7-dioxaspiro[5.6]dodecane 253 (C I IH2002) This is a component of the volatile secretion from the mandibular glands of a bee (Andrena haemorrhoa). 155 Both (2R,6S)-253 and (2S,6R)-253 were synthesized by Mori and Katsurada (Scheme 9 7 3 , starting from the enantiomers

'

0

. Similarly :

.

1

OH &C02Et (2S.6R) .253 [alD2' - 105' (pentme)

Scheme 975

' (80%)

478

The Synthesis of Insect Pheromones, 1979-1989

of ethyl 3 - h y d r o ~ y b u t a n o a t e .Due ' ~ ~ ~to the oxygen anomeric effect, 253 was obtained as a single isomer.

22. NITROGEN HETEROCYCLES AND SULFUR-CONTAINING COMPOUNDS AS PHEROMONES A. Danaidone (2,3-Dihydro-7-methyl-lH-pyrrolizin-l-one) 254 (C8H90N), Danaidal (l-Formyl-6,7-dihydro-5H-pyrrolizine) 255 (C8H90N), and Hydroxydanaidal (l-Forrnyl-6,7-dihydro-SHpyrrolizin-7-01) 256 (C8H902N) These are pheromones secreted by several male butterflies and moths such as the African monarch (Danaus chrysippus), the queen butterfly (D. gilippus berenice), Creatonotos gangis, and C. transiens (Scheme 976). I2O9* ' * l o They are biosynthesized from pyrrolizine alkaloids in plants ingested by them. 1209al 2 I o A synthesis of danaidal 255 was reported by Roder et al. (Scheme 976).'211An

& $ & & OH

Denaidone 254

Danaidal 255

CHO

Hydroxy danaidal 256

CHO

or S. A (42%)

(83%)

(45%)

255 m.p.60°C

Scheme 976

Arctiid moth (Cissepsfilvicollis) was attracted by both (R)-256and (S)-256.I2l2 Cisseps, Ctenuchu, and Hulysidota moths were all attracted by both the enantiomers of 256, the (S)-isomer having been the more

B. (3R,SS,9S)-Monomorine I (5-Methyl-3-butyloctahydroindolizine) 257 (cI 3H25N) This is a trail pheromone of the Pharaoh's ant (Monornorium pharuonis). I 2 l 3 The natural (+)-257was shown to possess the 3R,SS,9S-configuration by the synthesis of (3S,5R,9R)-(-)-257 by Royer and Husson. I 2 l 4 Macdonald synthesized an isomer of 257 starting from pyrroline urethane A (Scheme 977). 1 2 1 5A biomimetic synthesis by Stevens and Lee yielded (f)-257

22. Nitrogen Heterocycles and Sulfur-Containing Compounds as Pheromones

A

479

(71%)

An isomer 01

(*I.

257

Scheme 977

stereoselectively (Scheme 978). I 2 l 6 Kibayashi and his co-workers synthesized

(k)- 257

Scheme 978

(f)-257 by intramolecular nitroso-Diels-Alder reaction (A -+ B) (Scheme 979). I 2 l 7 . I 2 l 8 Their final step was unfortunately not selective, and the epimer D was also obtained as the minor product. A short synthesis of (&)-257 was reported by Kawanishi and his co-workers by using their highly regioselective a-alkynylation reaction of 1-methoxycarbonyl-2-methylpyridinium chloride with a Grignard reagent (A -+ B) as shown in Scheme 980.'2'9 Another short synthesis by Jefford et al. delivered (+)-257 in only six steps in an overall yield of 26% (Scheme 981).'220The key features were the regiospecific one-step assembly of the ring system from a suitably substituted pyrrole and its subsequent reduction to all-cis-substituted octahydroindolizine intermediate. The first enantioselective synthesis of the antipode [(3S,5R,9R)-(-)-257] of monomorine I was reported by Royer and Husson (Scheme 982).I2l4They used (R)-(-)-phenylglycinol as the chiral building block. The natural ( +)-monomorine I 2 5 7 was synthesized from diethyl L-( +)-tartrate by Yamazaki and Kibayashi as shown in Scheme 983. ' 2 2 1

480

The Synthesis of Insect Pheromones, 1979-1989

A

(k).257

Scheme 979

B

D ( 15%)

C

22. Nitrogen Heterocycles and Sulfur-Containing Compounds as Pheromones

A

B minor product (A:B - 4 : l )

481

7:l

0 [a)D"-35.80(hexane) el. Natural 257 (a]D"+46.50(hexane) (-)-257

Scheme 982

OMOM

1) n.BuMgBr/E$O 2) Swetn oxidn

P

(94%)

1) LiBH(s-Bu)pHF 2) N,H,+l,O/EIOH 3) PhCH,OCOCI.Na.$O, (66%)

hMOMO C

H 0

mH .Ph,P

Zn(BH,), 2

0

A (95%)

0

F PhCHzO& hKMO A

MOM0

OH OMOM NHCbr

>

EO2CN=NCOZEVrHF

HO

2)KOb'nHF (83%)

Scheme 983

OMOM

Cbz

1) HCI.MeOH

2) b i l l i m i d e z o l e Ph,P/tduera (8%)

482

The Synthesis of Insect Pheromones, 1979-1989

C. 2-Methyld-vinylpyrazine 258 (C7H8N2) This is the male-produced sex pheromone of the papaya fruit fly, Toxotrypana curvicauda. '222 Churnan et al. synthesized 258 as shown in Scheme 984, start-

ing from 2,6-dimethylpyrazine. "" It should be added that 2,5-dimethylpyrazine and 3-ethyl-2,5-dimethyl-pyrazinewere identified as trail pheromones of ants.'223

D. 2-sec-Butyl-4,5-dihydrothiazole259 (C,H,,NS) In combination with exo-7-ethyl-6,8-dioxabicyclo[3.2.l]oct-3-ene233, this functions as a chemical signal of the male state and a potential multi-purpose pheromone of the house mouse (Mus musculus).lo'* Both the enantiomers of 259 were synthesized by Masaki et al. (Scheme 985).'224 The absolute configuration of the natural compound has yet to be established.

(43%)

Scheme 985

(S)-259

[aJD"+15.80[CHCI,)

22. Nitrogen Heterocycles and Sulfur-Containing Compounds as Pheromones 1) I-BuSiMe,CI. imidazole 2) (i-Bu)*lH / THF

OH

k C 0 z M e

Ok!{

3) (COC1)2.DMSO, E$N / C H C l d (75%)

+

ACHo CH,Ci,

_ - A

(80%)

-

(8%)

I

3) (COCI),, DMSO, E$N / CH2CIz

483

1) M e O e O H ,Ph,P

)HC-oooMe 1) Ph,P-CHCO,Me/

CHZCI,

2) (I.Bu)PIH/THF

P

HO

(87%)

.-(+)-DET, I.Bu00H

>

rl(opt). / cH,ci,

Na(AI(OCH,CH20Me),H,1

HO

0

nu

0

0

M

e

loluene

>

(90%)

2) NaCN I DMF (92%)

i)CH,Ph

0

A+B

P h S - O o O MOCH,Ph B

1) (9BBN)OTf, (i-Pr),NEI/ CHzCIZ H202IM O H 2) m H / MeOH aq; NaOH (75%)

B

OCH,Ph C

bs OPiv

c

+

PivO

OPiv PivO p w

o

1) NaOMe / MeOH 2) PhCH,&.NaH/ DMF

F

*ooo"

OPlV

D

0

OCH,Ph

C

4)

c q

IWCN-H,b

('3%)

kH2Ph

,"ty OH

H,NCH,CH,SO,H.NaOH/MeOH h

3) Ce(NH,),(NO,),

0

,

H

2) H,,Pd-C/MeOH

&H2Ph

>

0

0

(8%)

OH

H

(8R,lSR)-260 [a)om-lQ.30(MeOH)

Scheme 986

484

The Synthesis of Insect Pheromones, 1979-1989

E. (15R)-2-{[15-(~-~-Glucopyranosyl)oxy]-8hydroxyhexadecanoyl]amino}ethanesulfonic Acid 260 (C24H4701

INS)

This is the oviposition-deterring pheromone secreted by females of the European cherry fruit fly (Rhugoletis cerusi), each of which lays one single egg into half-ripe cherries. ’*” Ernst and Wagner synthesized the four stereoisomers: (8R,15R)-, (8S, 15R)-,( 8 R , I S ) - , and (8S, 15S)-260.1226 By comparing the ‘HNMR spectra of the synthetic four isomers with that of the natural 260, the configuration at C-15 was determined as R . Scheme 986 illustrates the synthesis of (8R,15R)-260.1226 Other isomers were prepared in the same manner.

23. CONCLUSION The synthesis of 260 pheromones (in Ref. 1, 96 pheromones were discussed) have been reviewed in this book. The survey of literature encompasses the period April 1979 to the end of February 1990. If I have overlooked any works, I apologize to any chemists in this area whose research and work have been inadvertently omitted. The most notable advance achieved in this decade has been a clearer understanding of the significance of chirality in pheromone perception. Scheme 987 summarizes the results obtained thus far. As can be seen from the Scheme, stereochemistry-pheromone activity relationships are quite complicated. Like other bioactive and chiral natural products, many of the chiral pheromones belong to category A of Scheme 987. In this group of pheromones, only one enantiomer is bioactive and no inhibitory action can be observed with the inactive antipode. However, other unusual cases exist, as shown in categories B through H. In group B, only one enantiomer is bioactive and the inactive antipode inhibits the action of the correct enantiomer. Especially in the case of the Japanese beetle pheromone as studied by Tumlinson, its racemate lacks biological activity due to the strong inhibition caused by the wrong enantiomer. In the case of the pheromones in group C, insects do not distinguish the stereoisomers. Thus, every stereoisomer of the German cockroach pheromone evokes the response of the male. Ipsdienol is the pheromone belonging to group D. Different species of Ips bark beetles use different enantiomcrs, and the chirality of the pheromone is quite important in establishing and maintaining a particular Zps species. Sulcatol is the pheromone in Group E, which requires both enantiomers for pheromone activity, as exemplified by the ambrosia beetle (Gnathotrichus sulcatus).

23. Conclusion

485

A. Only one enanticmet is tiwaive. and ltm anrpode does not

6. Only one enanliomer in Mwdive, but the antipode or diarmreomer

C. All he rlermtsomem we bbactiva

D. Even In the m e @nus &Herent species use dHerent

inhibil the emon 01 Ihe phermone.

German mokoach

inhibils me W o n 01 me phemmone.

8n an tiamem.

etc

F

rnb one enanlwmer 16 86 atdve as me netural pheromone.

bul ib aawiry can be enhanmci by h e etdilwn 01 a less BEPW

s1ermoomer

(unnalural and less adve)

(naNrrd pheranone) red flour beem

G One enanuomer ~bactwe on male i ~ f f i L 0 while . he other IS

H. Only me =isomer

is active.

acwe on lemales

Scheme 981

Groups F, G , and H are also interesting, especially in the case of the olive fruit fly pheromone, whose R-isomer is active on males, while the other is active on females. Only the rneso-isomer of the tsetse fly pheromone was bioactive. As summarized above, the relationships between stereochemistry and pheromone activity are complicated. The precise meaning of this diversity may be clarified only after more extensive investigation of the nature of pheromone perception by insects.

486

The Synthesis of Insect Pheromones, 1979-1989

ACKNOWLEDGMENTS I thank my co-workers at the Laboratory of Organic Chemistry, Faculty of Agriculture, at the University of Tokyo, for the preparation of the Schemes. I also thank my wife, Keiko Mori, for typing the manuscript.

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41. 42. 43. 44.

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1098. Plaumann, D . E.; Fitzsimmons, B. J.; Ritchie, B. M.; Fraser-Reid, B. J . Org. Chern. 1982, 47, 941. 1099. Lagrange, A.; Olesker, A.; Costa, S . ; Lukacs, G.; Thang, T. T. Carbohyd. Res. 1982, 110, 159. 1100. Mori, M.; Chuman, T . ; Kato, K. Carbohyd. Res. 1984, 129, 73. 1101. Mulzer, J.; de Lasalle, P.; Freissler, A. Liebigs Ann. Cherri. 1986, 1152. 1102. LarchevZque, M . ; Henrot, S. Tetrahedron. 1987, 43, 2303. 1103. Hoffmann, R. W.; Helhig. W . Chern. Ber. 1981, 114, 2802. 1104. Helhig, W . Liebigs Ariri. Chern. 1984, 1165. 1105. Mori, K.; Seu, Y.-B. Tetrahedron. 1988, 44, 1035. 1106. Chong, J. M . ; Wong, S.J . Org. Cheat. 1987, 52, 2596. 1107. Sinnwell, V . ; Schulz, S.; Francke, W . ; Kittmann, R.; Schneider, D. Tetrahedrori Lett. 1985, 26, 1707. 1108. De Shong, P.; Lin, M.-T.; Perez, J . J . Tetrahedrori Lett. 1986, 27, 2091, 1109. Schulz, S.; Francke, W.; Konig. W. A.; Schurig, V . ; Mori, K.; Kittmann, R.; Schneider, D. J . C h i . Ecol. 1990, 16, 351 1. 1 110. Heemann, V . ; Francke, W. Natur~visserischafen,1976, 63, 344. 1111. Redlich, H.; Schneider, B.; Francke, W. Tetrahedron Lett. 1980,21, 3009. 1112. Redlich, H . ; Schneider, B.;Francke, W. Tetrahedrori Lett. 1980, 21. 3013. I 1 13. Redlich, H.; Schneider, B.; Hoffmann, R. W.; Geueke. K.-J. Liebigs Ann. Cherrt. 1983, 393. I 1 14. Sato, 'I,.; Itoh, T.; Hattori, C.; Fujisawa, T. Chern. Lett. 1983, 1391. 1115. Kongkathip, B.; Kongkathip, N. Tetrahedrori Lett. 1984, 25, 2175. I 1 16. Guindon, Y.; St. Denis, Y.; Daigneault, S . ; Morton, H. E. Tetruhedrori Lett. 1986, 27, 1237. 1117. Page, P. C. B.; Rayner, C . M.; Sutherland, 1. 0. Tetrahedron Lett. 1986, 27, 3535. 1 118. Mohr, P.; Tamm, C . Tetrahedron Lett. 1987, 28, 395. I 1 19. Adams, J.; Frenette, R. Tetrahedroii Letr. 1987, 28, 4773. 1120. Borden, J. H . ; Handley, J . R.; Johnston, B. D . ; MacConnell, J . G . ; Silverstein, R. M.; Slessor, K . N.; Swigar, A . A.; Wong, D. T. W. J . Cherri. Ecol. 1979, 5, 681. 1121. McKay, W .R.; Ounsworth, J.; Sum, P.-E.; Weiler, L. Carl. J . Cherrf. 1982, 60,872. 1122. White, J . D.; Avery, M. A.; Carter, J . P.J . Am. Cherri. Soc. 1982, 104, 5486. 1123. Skattehdl, L . ; Stenstrdm. Y. Tetrahedrori Lett. 1983, 24, 3021. 1124. Skattehdl, L.; Stenstrdm, Y. Acta Chern. Scarid. 1985, B39, 291. 1125. Johnston, B. D.; Slessor, K . N.; Ochlschlager, A. C . J . Org. Cherri. 1985, 50, 114. 1126. Mori, K . ; Sasaki, M. Tetrahedron. 1980, 36, 2193. 1127. Slessor, K. N . ; Oehlschlager, A. C . ; Johnston, B. D.; Pierce, Jr.; H. D.; Grewal, S. K.; Wickremesinghe, K. G . J . Org. Cherri. 1980, 45, 2290. 1128. Mori, K.; Uematsu, T.; Minohe, M.; Yanagi, K. Tetrahedrori Lett. 1982, 23, 1921. 1129. Mori, K.; Uematsu, T.; Minohe, M.; Yanagi, K. Tetrahedron. 1983,39, 1735. 1130. Kandil, A . A.; Slessor, K. N. J . Org. Cherri. 1985, 50, 5649. 1131. Kluge, A. F. Heterocycles. 1986, 24, 1699. 1132. Perron, F.; Albizati, K. F. Chern. Rev. 1989, 89, 1617. 1133. Francke, W.; Reith, W.; Sinnwell, V . Chern. Ber. 1980, l l 3 , 2686.

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The Total Synthesis of Natural Products, Volume9 Edited by John ApSlmon Copyright © 1992 by John Wiley & Sons, Inc.

Subject Index Acanfhoscelides obfectus, 2 12 Acarid mite, 116 3-Acetoxy-2,6-dimethyl- 1 ,5-heptadiene,(R), 286 6-Acetoxy-5-hexadecanolide,(5R,6S), 252 3-Acetoxy-7-methyl-6-nonene,(3R, 6E), 285 Achroia grisella, 138 Adoxophyesfascia fa, 36 Adoxophyes orana, 36 Adoxophyses species, I19 African monarch butterfly, 318, 478 African sugarcane borer, 348 Agroniyra frontella, 9 Agrotis segerurn, 25 Alfalfa blotch leafminer, 9 Allofarnesene,(Z, Z, Z ) , 276 Almond moth, 69 Alsophila potnetaria, 79, 8 1 Alsophila quadripuncfafa, 80 Arnathes c-nigruni, 34 Ambrosia beetle, 280 American cockroach, 336, 341, 343 Amyelois transitella, 134 Anasfrepha ludens, 360 Anasrrepha suspensa, 360, 362 Anastrephin, 360 Andreno haemorrhoa. 449, 459, 461, 477 Andrena wilkella, 449, 471, 476 Anobium punctatutn, 377 Anorriala rufocuprea, 2 10 Ant, 101 Ant lion(s), I I I , 374

Aiitheraea polyphenius, 70 Anthonoinus grandis, 303, 3 17, 334 Anfhrerius verbasci, 2 10 Anticarsia geniniatalis, 82 Aonidiella auranti, 320 Aoriidiella cifrina, 326 Aphis gossypii, 274 Aphornia gularis, 226 Apple clearwing moth, 78 Apple leafminer moth, 36 Archips seniifcranus, 24, 37 Arctiid moth, 66, 83, 478 Arcfiidae, 66 Argentine ant, 132 Asian corn borer moth, 24 Atlagenus elongatulus, 2 12 Attagenus niegafonia, 2 I 1 Atta texana, I77 Australian fruit fly, 473 Azuki bean weevil, 345 Bagworm moth, 101 Banded cucumber beetle, 185 Bark beetle, 303. 370, 371 Bishomomanicone, 179 Black carpet beetle, 21 I Blattella germanica, 185 Boarniia selenaria, 79 Boll weevil, 317, 334 Bombykol [ 10,12-hexadecadien-l-oI], (IOE,12Z), 59 Bornbyx inori, 59 523

524

Subject Index

Bontebook, 157 Brachrnia ntacroscopa, 25 Bredius maridibularis, 234 endo-Brevicomin,( IR,5S,7S), 394 exo-Brevicomin,( IR,5S,7R), 394 2-sec-Butyl-4,5-dihydrothiazole, 482 2-Butyl-8-methyl- 1,7dioxaspiro[5.5]undecane, 475 Cabbage looper, 26 Cabbage moth, 25, 37 Cabbage webworm, 134 California five-spined ips, 294 California red scale, 320 Callosobruclnts chinensis, 345 Callosobruchusic acid, 345 Cartipotlotus herculeanus, 232 Canipoiiotus rtoveboracerisis, 232 Canipotiotus penrrsylvarricits. 232 Canadian red-sided garter snake, 175 Caribbean fruit fly, 360, 362 Carob moth, 132 Carpenter ants, 232 Carpenter bee, 220 Carpenter worm moth, 55 Carpo.ria niporlensis, I58 Cathartus quadricollis, 285 Cedra caurello, 69 Ceratiris capitata, 18 Cereal tortix moth, 23 Chalcogran, 209, 446 Chenytree borer, 78 Chilo srtppressalis, 133, 139 Cigarette beetle, 193, 379 Cisseps fulvicollis, 478 Citrus flower moth, 131 Citrus mealy bug, 312 Cleunving moth, 74 Ctrephasia punricatra, 23 Cocoa pod borer, 84 Codling moth, 48 Common furniture beetle, 377 Common wasp, 45 1 , 455 Comstock mealybug, 286 Confused flour beetle, 141 Conophthorus sp., 455 Conopotirorpha cramerella, 84 Corcyra cephalonica, 330, 336 Cossus cossus, 69 Cotton aphid, 274

Cotton boll weevil, 303 Cotton boll worm, 133 Cotton leafworm, 56 Creatonotos gangis, 79, 95, 478 Creatonotos transiens, 79, 95, 478 Cremamgasrer, 178 Creniatogaster castanea, 108 Crernarogaster lienqniei, 108 Cryptolesfesferrugineus, 265, 364 Crypiolestes piisillus, 265, 270 Cryptolestes turcicus, 270, 27 I Cryptophlevia leucoreta, 20 Cucumber fly, 459, 471 Culex pipieris fatigaris, 252 Culex tarsalis, 264 Cylas fortnicarius elegantirlits, 20 1

Dacus cacitttiiiiatits, 470 Dacits cuctimis, 459, 471 Dacus cucurbitae, 18, 233 Dacus dorsalis, 473 Dacus halfordiae, 193, 471 Dacits latijirons, 473, 475 Dacus occipitalis, 193, 473 Dacus oleae, 462 Darrialiscus dorcas dorcas, 157 Danaidal, 478 Danaidone, 478 Dariaus chrysippus, 318, 478 Danaus gilippus berenice, 478, 320 Danaus plexipptis, 346, 347, 380

2,4,6-Decalrien-5-olide,(2Z,4Z,6E), 230

5-Decenyl acetate.(Z), 28 5-Decenyl isovalerate,(Z), 160 Dendroctorius bretdcomis, 38 I , 394 Dendroctonus frontalis, 38 I , 394 Dendroctonus pseudotsugae. 3 15, 3 16, 38 I Detidrolittius punctafus, 38 Dendrolitnus speciabillis. 38, 41 Deodar weevil, 333 Dermestid beetles, 152, 216 Diabrotica balteata, 185 Diabrotica barberi, I13 Diabrotica lotigicornis, I 13 Diabrotica porracea, I13 Diabrotica undeciinpunctata horvardi. I8 I Diabroiica virgifera virgifera, 1 13 Diabrotica virgifera zeae, I13 Diamond black moth, 37 Dichocrocis puiicriferalis, 133

Subject Index

525

7, 1-Dimethyl-3-methylene-1,6,10dodecatriene,(E), 274 3, I-Dimethyl-2-nonacosanone,(3S, 1 IS), 185 2,3-Dihydro-3,5-dimelhyl-2-ethyl-6-( I 'methyI-2'-hydroxoybutyI)-4H-pyran-one, 3, -Dimethylnonadecane,9 379,380 I ,7-Dimethylnonylpropanoate, 113 2,3-Dihydro-2-isopropyl-2,5-dimethylfuran, 3,7-Dimethyl-2,6-octadienyl formate,(Z), 29I 3,7-Dimethyl-2,7-octadienylpropanoate,(E), 371 291 2,3-Dihydro-7-1nethylI H-pyrrolizin-1-one, 3,7-Dimethyl-2,7-octadienyl propanoate,(Z), 478 291 2,3-Dihydro-2,3,5-trimethyl-6-( I '-1nethyl-23.7-Dimethyl-2-octeneI ,I-dioicacid,@), 345 oxobutyl)-4H-pyran-4-one, 374 ,8-diol,(E), 3 18 2,3-Dihydro-2,3,5-trimethyl-6-(2'-hydroxy-l-3.7-Dimethyl-2-octene-l 3,7-Dimethyl-6-octen-4-olide,(3S,4R), 348 methylbutyl)-4H-pyran-4-one,378 4,6-Dimethyl-4-octen-3-one,(4E,6S), 179 3,3-Dimethyl-A'~P-cyclohexaneethanol,(E), 6,12-Dimethyl-2-pentadecanone,(6R, 12R), 334 I ,7-Diethyl1,6-dioxaspiro[4.4]nonane,449 Dihydroactinidiolide,(R), 356

3,3-Dimethyl-A',P-cyclohexaneethanoI,(Z),

317 4,8-Dimethyl-3,8-decadienIO-olide,(3E,IE), 362 4,8-Dimethyl-4,8-decadienIO-olide,(4E,8E), 364 3,7-Dimethyl-2,6-decadieneI , l0,dioic acid,(2E,6E), 347 3,7-Dimethyl-2,6-decadiene-l, 10dio1,(2E,6E), 320 4,8-Dimethyldecanal(triborlure),(4R,8A),141 I ,3-Dimethyl-2,9-dioxabicyclo[3.3. I)nonane, 435 I ,5-Dimethyl-6,8-dioxabicyclo[3.2. lloctane, 381 1,6-dioxaspiro[4.6]undecane, 2,7-Dirnethyl461 2,8-DirnethylI ,7-dioxaspiro[5.5]undecane, (2S,6R,8S),470 2.8-Dimethyl-I ,7-dioxaspiro[5,5]undecane-401, 476 1,8-Dimethyl-3-ethyl-2,9-

dioxabicyclo[3.3.I]non-7-ene,(IR,3S,5S), 435

I ,S-Dimethyl-3-ethyl-2,9-

dioxabicyclo[3.3.l]non-7-en-6one,(lR,3S,SR), 435 2,4-Dimethyl-5-ethyI-6,8dioxabicyclol3.2.Iloctane,428 5,9-Dimethylheptadecane,5S, 9.9, 8

3,6-DimethyI-2,4-heptanedione, 176

2,6-DimethyI-5-heptenal, 157 17,21-Dirnethylhep1atriacontane-~neso,13 3,5-Dimethyl-6-( I '-methylbuty1)-tetrahydro2H-pyran-2-one,(3R,SR,6S, I 'R),227

185

15,23-Dirnethylpentatriacontane-meso,12 15,19-Dimethyltritriacontane, 10 I ,7-Dioxaspiro[S.51undecane,462

Diparopsis castanea, 23, 50 Diprion sirnilis, 128

I ,7-Dipropyl1,6-dioxaspiro[4.4]nonane,449 Disparlure, 85 3,6-Dodecadien-l l-olide,(32,6Z,I IR), 268 3,6-Dodecadien12-olide,(3Z,6Z), 267 5,7-Dodecadienal,(SE,72),I31 5,7-Dodecadienl-o1,(5Z,7E), 38 5,7-DodecadienI-o1,(5Z,7Z), 4I 8,IO-Dodecadien-1-01,( 8 E ,1O E ), 48 8.IO-Dodecadien-I-o1,(8Z, IOE), 49 7-9-Dodecadienylacetate,(7E,9Z), 42 9,lI-Dodecadienylacetate,@), 50 9,lI-Dodecadienylacetate,($), 54 4-Dodecanolide,234 3,6,8-Dodecatrien-I-o1,(3Z,6Z,8E). 84

3-Dodecen-ll-olide,(3Z,IIS),265 3-Dodecen-12-olide,(Z),265 . 7-Dodecenyl acetate,(E)-, 20 7-Dodecenyl acetate,(Z)-, 29 8-Dodecenylacetate,@)-, 2 I 8-Dodecenyl acetate,(Z)-, 3 I 9-Dodecenylacetate,@)-, 23 9-Dodeceny l acetate,(Z)-, 32 3-Dodecenyl(E)-2-butenoate,(Z),201 Dominicalure I , 99 Dominicalure 2 , 99 Douglas fir beetle, 315,316,381 Douglas fir tussock moth, 165 Dried bean beetle,212 Drosophila busckii, 130

526

Subject Index

Drosophila malerkotliana, 37 Drosophila inelanogasfer, 66 Drosophila tnulleri, 122, 158 Drugstore beetle, 374, 378 Dryocetes confusus, 394 Dryocetes autographus, 394 Earias insulana, 133 Earias vittella, 138 Eastem subterranean termite, 84 Eastem spruce budworm, 132 Ectotnyelois ceratoniae, 132 Eight-toothed engraver beetle, 296 Egyptian cotton leafworm, 56, 139 Eldatra saccharina, 348 Elm bark beetle, 370 Engelmann spruce weevil, 332 Epianastrephin, 360 Epiphyas posfwittana, 56 9, IO-Epoxy-3,6henicosadiene,(32,62,9S,10R), 95 9.10-Ep0~y-l,3,6henicosatriene,(3Z,6Z,9S,IOR), 98

9,10-Epoxy-6-henicosene,(6Z,9S, IOR), 94 IOR), 9,lO-Epoxy-1,3,6-icosatriene,(32,6Z,9S, 98 2-(3’,4’-Epoxy-4’-methylcyclohexy)-6methylhepta-2,5-

diene,(l’S,3’R,4’S,Z),(3’S,4’R), 33 I 7,8-Epoxy-2-methyloctadecane,(7R,8S), 85

9,IO-Epoxytetrahydroedulan, (1R,2S,4S,7R,IOS),380 En silkworm, 138

2-Ethyl-8-methyl-1,7dioxaspiro[5.Slundecane, 473 I-Ethylpropyl (2S,3R)-2-methyl-3hydroxypentanoate, 203 Euploea boisdrrvalii, 380 Euploea eusipires, 280 Euploea klugii, 380 Euploea leucosfioos, 380 Euploea mulciber, 380 Euploea fulliolus, 380 Eupoecilia (Clysia) atnbigitella, 32 Euroleorr nostras Crocus bore, I 1 I European cherry fruit fly, 484 European goat moth, 69 European grape beny moth, 3 I European pine sawfly, 128 European pine shoot moth, 23 Fall armyworm, 36 Fall cankerworm moth, 79, 81 Fall webworm moth, 98 False codling moth, 20 Faranal, 148 Farnesal,(E,E), 336 Farnesal, (Z,E), 336 a-Famesene,(E,E), 273 a-Femesene,(Z,E), 273 @-Farnesene,(E),274 Fermlacetone 11, 265 Ferrulactone I, 364 Flat grain beetle, 265, 270 Forest tent caterpillar, 38 Fortnicu polycletra, 202 Formica rufa, 202

Esfigtnene acrea, 95 2-Ethyl-I ,6-dioxaspiro[4.4]nonane,446

l-Formyl-6,7-dihydro-5H-pyrrolizine, 478 1-Formyl-6,7-dihydro-5H-pyrrolizin-7-ol, 478

one,(R), 367 2-Ethyl-6-methyl-2,3-dihydro-4H-pyran-4one,@), 367 errdo-7-Ethyl-5-methyl-6,8dioxabicyclo[3.2.lloctane, 394 exo-7-Ethyl-5-methyl-6.8dioxabicyclo[3.2.Iloctane, 394 exo-7-Ethyl-5-methyl-6.8diaxabicyclo[3.2.I]oct-3-ene, 424 2-Ethyl-7-methyl-1,6-dioxaspiro[4.5]decane, 459 7-Ethyl-2-methyl-1,6-dioxaspiro[4.5]decane, 459

Fruit fly, 67, 193

2-Ethyl-2-methyl-2.3-dihydro-4H-pyran-4- Frontalin,(lS,SR), 381

Geometrid moth(s), 66, 80 Geornetriidae, 66 Geman cockroach, 185 Giant looper, 79 Glossina rnorsitans morsfians, I3 Glossina pallidipes, 12, I3 Goasyplure, 71 ( l5R)-2-{[ I ~-9-D-G~ucopyranosy~)oxy]-8hydroxyhexadecanoy llamino }ethanesulfonic acid, 484 Glyphodes pyloalis, 84

Subject Index

Gnathatrichus sulcatus, 280 Goumois grain moth, 73 Grain beetle, 270, 271 Granary weevil, 203 Grandisal, 332 Grandisol, 303 Grape borer, 109, 191 Grape berry moth, 33 Grape root borer, 74 Grape vine moth, 42 Grapholiia niolesta, 2 I Grapholitha molesta, 3 I Green bug, 364 Green stink bug, 33 I Grocus bore, 374 Gypsy moth, 85 Heart and dart moth, 33, 36 Hedya ochroleucana, 49 Helioihis antrigera, 133 Helioihis virescens, 133 Hellula utidalis, 134

3,6-Henicosadiene,(32,62), 66 6,9-Henicosadiene,(6Z,9Z), 66

1,6-Henicosadien-l I-one,(Z), 165 I ,3,6,9-Henicosatetraene,(3Z,6Z.92), 83 3.6,9-Henicosatriene,(3Z,62,9Z), 82 6-Henicosen-1 I-one,(Z), 165 Hepialone, 367 Hepialus californicus, 367 Hepialus hecia, 368, 435 7 , l I-Heptacosadiene,(7Z, 1 IZ), 67 IO-Heptadecen-2-one,(Z),158

I I-Hexadecen- 13-ynyl-acetate,(Z), 63 13-Hexadecen-l I-ynyl-acetate,(Z), 61 I I-Hexadecenyl acetate, ( E ) , 25 1 I-Hexadecenyl acetate, (Z), 37 11,13-Hexadecadienyl acetate,(l IZ, 13E), 63 4-Hexanolide, 216 Holomelina aurantiaca, 8 Homofarnesene,(E,E), 277 Homo farnesene, (Z,E), 277 Homomanicone, 179 10-Homonerol oxide, 374 Honeybee, 203, 204 House fly, 25 House mouse, 425, 482 Hydroxydanaidal, 478 9-Hydroxy-2-decenoic acid,@), 203

IO-Hydroxy-3,7-dimethy1-2,6-decadienoic

acid,(2E,6E), 346 29-Hydroxyl-3,l I-dimethyl-2nonacosanone,(3S,l IS), 185

7-Hydroxy-4,6-dimethyl-3-nonanone,

(4S,6S,6S), 193 3-Hydroxy- 1,7-dioxaspiro[5. Slundecane, 462 4-Hydroxy- 1,7-dioxaspiro[5 .S]undecane, 462 2 4 1-Hydroxy- 1-methylethyI)-5methyltetrahydrofuran,cis,370 2 4 I -Hydroxy- I -methylethyl)-5methyltetrahydrofuran,trans, 370 5-Hydroxy-4-methyl-3-heptanone,(4S,5R), I89 2-Hydroxy-3-octanone,(S),191 Hylecoetrrs dermesioides, 37 I Hyphaniria cunea, 95, 98

5-(3E,6-Heptadienyl)-dihydro-2(3H)-furanone, 3,6,9-Icosatrien,(3Z,6Z,9Z), 82 233 5-Hexadecanolide,(R), 242

10,12-Hexadecadienal,(IOE~ 12E). 133

I1,13-Hexadecadienal,( IIE,13E), 134 I1,13-Hexadecadienal,(I 1Z,132), 134 6,1 I-Hexadecadienyl acetate,(6E, I IZ), 70 7, I I-Hexadecadienyl acetate,(7Z, 1 I Z ) , 71 7,11-Hexadecadienyl acetate,(7Z,I I E ) , 71 I IZ), 138 4,6,1 I-Hexadecatrienal,(4E,6E, 4,6,lO-Hexadecatrienyl acetate,(4E,6E, IOZ), 84 4.6.10-Hexadecatrienyl acetate,(4E,62, IOZ), 84 7-Hexadecenal,(Z), 132 1 I-Hexadecenal,(Z), 133

527

13-Icosen- IO-one,(Z), 158 1 I-Icosenyl acetate,(Z), 37 Indian meal moth, 69 Introduced pine sawfly, 128 Invictolide, 227 Ipsdienol, 294 Ipsenol, 294 Ips paracot?firsus, 294 Ips pirii, 295 Ips typographus, 296 Iridomynnex huriiilis, I32 Iris borer, 133 Isopenplanone-A, 341 3-lsopropenyl-2,2-dimethylcyclobutanemethyl acetate,(lR,3R), 312

528

Subject Index

1-1sopropenyl- 1-methycyclobutaneethanal,cis-,

303. 332

Japanese beetle, 238 Khapra beetle, 152, 216 Lardoglyphus konoi, 116

Lardolure, I16 Lasioderma serricorne, 193, 379 Laspeyresia pomonella, 48

Leaf-cutting ant, 177 Leopard moth, 74 Lepfogenys diminufa, 101

Lesser grain borer, 99 Lesser peachtree borer, 75 Ducatiia separata, I33 Leucopiera sciiella, 8 Light-brown apple moth, 56 Lineatin,( IR,4S.W,7R), 436 Lobesia boirana, 42 Lymaniria dispar, 85 Lyonefia clerkella, 15

Macronocrua onusfa, 133

Maize weevil. 189 Malacosoma dissrria, 38

Male monarchy butterfly, 347 Mattiestra brassicae, 25 Manica bradleyi, 179 Manica tnutica, 176, I79 Manicu rubida, 179

Manicone, ( S ) , 179 Mafsucossus tnafsumurae, 184 Mafsucoccus resinosae, 184 Mafsucocciis fhunbergianae, 184

Matsuone, 184 Mediterranean fruit fly, 18 Megarhyssa norioni nortoni, 459, 471 Megaselia halferafa, 177

Megatomoic acid, 2 1 I

Megoltra viciae, 364 Melacosoma californicum, 13 1 Meliffia satyriniformis, 74

Melon fly, 18, 233 I-Methylbutyl decanoate,(R), 101

I-MethyIbutyl(E)-2,4-dimethyl-2pentenoate,(S), 99

I-Methylbutyl(E)-2-methyl-2-pentenoate,(S), 99 5-Methyl-3-butyloctahydroindolizine, 478 I-Methyl-2-cyclohexen- 1-01, 3 16 3-Methyl-2-cyclohexen-1-01. 3 15 Methyl (2E,42)-2,4-decadienoate, 209 2-Methyl- 1,6-dioxaspir0[4.5]decane,45 1 7-Methyl-I ,6-dioxaspiro[4.5]decane,455 2-Methyl- 1,7-dioxaspiro[5.6]dodecane,477 1-Methyldodecyl acetate,@), 122 10-Methyldodecyl acetate, I19 4-Methyl-3-heptanol,(3S,4S), 101 2-Methylheptadecane, 8 4-Methyl-3-heptanone,(S),177 6-Methyl-5-hepten-2-01, 280 14-Methyl-8-hexadecena1, 152

4-Methyl-3-hexanol,(3R,4S), 101

2-Methyl-5-hexanolide,cis, 220 4-Methyl-3-hexanone,(S),176 3-Methyl-6-isopropenyl-3,9-decadienyl acetate,(R,Z), 320 3-Methyl-6-isopropenyl-9-decenyl acetate,(3S,6R), 320 3,9-Dimethyl-6-isopropenyl-3,9-decadienyl proponoate,(R,Z), 330 3,9-Dimethyl-6-isopropyl-5,8-decadienyl acetate,(S,E), 326 Methyl 3-isopropylpentanoate, 202 2-Methyl-6-methylene-2,7-octadien-4-ol, 294 2-Methyl-6-methylene-7-octen-4-ol, 294 7-Methyl-3-methylene-7-octenyl proponoate,(Z), 291 4-Methyl-l-nonanol,(R), I I I

14-Methyl-I-octadecene-(b),15 6-Methyl-3-octanone, 178 2 I2 Methyl (R,E)-2,4,5-tetradecatrienoate, Methyl (Z)-5-tetradecenoate, 2 10 I-Methyltetradecyl acetate.(S), 130 IO-Methyl-2-tridecanone,(R), 181 15-Methyltritricontane, 10 2-Methyl-6-vinylpyrazine, 482 Muscalure, 9-tricosene,(Z), 25 Mexican corn rootworm, 113 Mexican fruit fly, 360 Mocis laripes, 82 Mold mite, 291 Momesrra brassicae, 37 Monarch butterfly, 346, 380 Monomorine 1,(3R,5S,9S), 478 Monomorium pharaonis, 148, 478 Mountain-ash bentwing, 8

Subject Index Mulberry pyralid, 84 a-Multistnatin,( IS,2R,4S,5R), 428 &Muhistriatin, 431, 433 Mushroom fly, 177 Mus musculus, 425, 482 Musca dornestica. 25 Myrmica ants, 108 Myrtnica rubra, 108 Myrrnica scabrinodis, 108 Nasutiternies exitosrts, 277 Nasutiternres graveolus, 277 Nasutitermes rvalkeri, 277 Naval orangeworm, 134 Neocembrene,(E,E,E), 277 Neodipriorr lecotrtei, f28 Neodiprion pinetum, I28 Neodiprion sertifer, 128

Nepetalactol,(lR,4aS,7S,7aR),364

Nepetalactone,(4aS,7S,7aR), 364 Neryl formate, 291 New Zealand leafroller moth, 34 Nezara viridula, 33 I 7,l l-Nonacosadiene,(7Z,IIZ), 67 6,9-Nonadecadien-3-one,(6Z,9Z), 165 3,6-Nonadecadiene,(32,62),66 3,6,9-Nonadecatnene,(32,6Z,9Z), 79 I ,3,6,9-Nonadecatetraene,(3Z,6Z,92), 81 3,6,9,1l-Nonadecatetraene,(32,62,92,I I E ) , 81 3,6,9, I l-Nonadecatetraene.(32,6Z,92,1IZ), 81 12-Nonadecen-9-one,(Z),158 2,6-Nonadien-4-oIide,(22,6Z), 226 6-Nonen-l-ol,(E), 18 6-Nonenyl acetate,(E), 18 Normanicone, 179 Northern corn rootworm, I13 Northern pine weevil, 332 Nostrenol,(R), 11 1 Nudaurelia cytherea cytherea, 160 Oak leafroller moth, 24, 37

Oak processionary moth, 63 2-Ochtoden-l-al,(E), 334 2-Ochtoden-1-al,(Z), 334 2-Ochtoden-l-ol,(Z), 3 17 3,13-Octadecadien-l-ol,(3E, 13Z), 76 2.13-Octadecadienyl acetate,(2E, 132). 74 3,13-Octadecadienyl acetate,(3E, 13Z), 76 3,13-Octadecadienyl acetate,(3Z,132). 74

529

1 I-Octadecenal,(Z), 138 13-Octadecenal,(Z), I39 2,3-0ctanedio1,(2S,3S), 109 3-Octano1, 108 Olive fruit fly, 462 Omniferous leafroller moth, 24 Qperophrhera brunrata, 8 1 Qrgyia pseudotsugata, I65 Oriental hornet, 242 Oriental fruit fly, 473 Oriental fruit moth, 21, 26 Qryzaephillus nrercutor, 265, 268 OrymephiNus surinamensis, 267, 268, 27 I Ostrina ficrnacalis, 24 9-0x0-2-decenoic acid,@), 204

2-0~0-4-ethenyI-4,7a-dimethyl-2,4,5,6,6,7a-

hexahydrobenzofuran, 360 6-Oxo-l-nonanol, 193 2-0~0-4,4,7a-trimethyl-2,4,5,6,6,7ahexahydrobenzofuran,(R), 356 Pharaoh’s ant, 148,478 Palaearctic bee, 449 Papaya fruit fly, 482 Paralobesia viteana. 33 Paranthrene tabaniforinis, 76 Parasitoid wasp, 459, 47 I Paravespula vulgaris, 45 1 455, 459 Peach fruit moth, 158 Peach miner moth, 15 Peach tree borer, 75 Pectinophora gossypiella, 7 I 7,1 I-Pentacosadiene,(7Z, I IZ), 67 230 6 4 I-Pentenyl)-2H-pyran-2-one),(E), Peribatodes rhomboidaria, 165 Penplanone-A,(-), 341 Penplanone-B,( -), 336 Penplanone-C, 343 Periplanone-D, 343 Periplaneta americana, 336, 341, 343 Phragrnatobia fuliginosa, 94 Phthoritriaea opercufelfa,68 Phyllonorycter ringotriella, 36 Pine bast scales. 184 Pine emperor moth, 160 Pine engraver, 295 Pine moth, 38, 41 Pink bollworm moth, 71 Pissodes approximatus, 332 Pissodes netnorensis, 333 Pissodes strobi, 332

530

Subject Index

Pifyogenes chalcographus, 209, 446 Pityol,cis, 370 Pityol,(2R,SS)-frans, 370 Pityophthorus pityographus, 303, 370 Ptanococcus cirri, 3 I2 Planotortrix excessana, 34 Platynora srultana, 24 Plirfella xylostella, 37, 133 Popilliu japoriicu, 238 Poplar twig clearwing moth, 76 Potato tubenvorm moth, 68 Prays cifri, I3 I Prinoxystus robiniae, 55 Processionary moth, 63, 64 Pseudaulucaspic pentagona, 330 Pseudococcirs comstocki, 286 Pfeleobirts viffatus,370, 37 I Purple stem borer, 37 Pyralid moth, 226 Quadruspirliotiisperniciosirs, 29 I Quadrilure, 285 Queen butterfly, 320, 478 Red bollworm moth, 21, 50 Red flour beetle, 141 Red-headed pine sawfly, 128 Red iniported fire ant, 227, 273, 276, 277, 356 Red wood ant, 202 Reficulirerniesjavipes, 84 Reficuliternies virginicus, 84 Rhagolefis cerasi, 484 Rhyucionia buoliana, 23 Rhyzopertha doniiirica, 99 Rice moth, 330, 336 Rice stem borer, 133, 139 Rice weevil, 189 Rove beetle, 234 Ruby tiger moth, 94 Rusty grain beetle, 265, 364 Salt marsh caterpillar moth, 95 Sarnia Cynthia ricini, 138 San Jose scale, 291 Sawtoothed grain beetle, 267 Sceliodes cordalis, 25 Schizaphis grantinurn, 364 Scolytus inulfistriatrrs, 101, 428

Scoria exclamafionis, 33, 36 Scrobipalpa heliopa, 23 Semcolone.(2S,3R, 1 ' R ) , 379 Serricornin, 193 Serricorole,(2S,3R, 1 'S,2'S), 380 Sesatnia irferens, 37 Seudenol, 315 Silkworm moth, 59 Sitophilate, 203 Sitophilure, 189 Sifophilrts granarius, 203 Sifophilus orytae, 189 Sifophilus zeamais, I89 Sifotroga cerealella, 73 Six-spinned spruce bark beetle, 209, 446 Smaller cleanving moth, 74 Smaller European elm bark beetle, 101, 428 Small forest ant, 202 Smaller tea trotrix moth, 36, 119 Solenopsis invicfa, 227, 230, 273, 276, 277, 356 Southern armyworm moth, 69 Southern corn rootworm, 181 Southern house mosquito, 252 Southern pine beetle, 394, 381 Soybean beetle, 210 Spiny bollworm, 133 Spodopfera eridiana 69 Spodoptera frrigiperda, 36 Spodoptera littoralis, 56, I38 Spodoptera litura, 56 Spotted bollworm, 138 Spotted cutworm moth, 34 Spruce bark beetle, 296 Square-necked grain beetle, 285 Squash vine borer, 7 Stable fly, 10 Stegobinone,(2S,3R, I'R), 374 Stegobiol,(2S,3R, I 'S,2'S), 378 Sfegobiurnpaniceurn, 374, 378 Stink bugs, 128 Sfirefrusanchorago, 128 Sfomrys calcitrans, 10 Striped ambrosia beetle, 435, 436 Subterranean termite, 84 Sulcatol, 280 Summerfruit tortrix moth, 36 Suspensolide, 362 Sweet potato leaf folder moth, 25 Sweet potato weevil, 201

Subject Index Swift moth, 368, 435 Synarirhedon acerrubri, 74 Synanrhedon exitiosa. 75 Synanrhedon hecror, 78 Synanrhedon myopaefortnis, 78 Synanrhedon pictipes, 75 Synanrhedon renuis, 74

Tenebrio molitor, I I 1 Termite, 277 9, I I-Tetradecadienal,(9Z,1 I E ) , 132 3,5-Tetradecadienoic acid,(3E,5Z), 21 I 33-Tetradecadienoic acid,(3Z,5Z), 2 12 5,s-Tetradecadien- I3-olide,(5Z,SZ, 13R), 27 1 3,5-Tetradecadienyl acetate,(3Z,5E), 55 9 3 , 13-Tetradecadieny l acetate,(Z), 69 9, I I-Tetradecadienyl acetate,(9E, I I E ) , 56 9,l I-Tetradecadienyl acetate,(92,1 IE), 56 9,12-Tetradecadienyl acetate,(92,12E), 69 9,11,13-Tetradecatrienal,(9Z,II E ) , 132 7-Tetradecenal,(Z), 13 I 9-Tetradecenal,(Z), 132 1 I-Tetradecenal,(E), 132 1 I-Tetradecenal,(Z), 132 5-Tetradecen-4-olide.(R.Z),238 5-Tetradecen- 13-olide,(5Z,13s). 269 5-Tetradecenyl acetate,(Z), 33 7-Tetradecenyl acetate,(Z), 34 9-Tetradecenyl acetate,(Z), 36 10-Tetradecenyl acetate,(Z), 36 1 I-Tetradecenyl acetate,(E), 24 1 I-Tetradecenyl acetate,(Z), 37 12-Tefradecenyl acetate,@), 24 Tetrahydro-2,2,6-trimethyl-2H-pyran-3ol,(3R,6S)-cis, 371 I ,3,5,7-Tetramethyldecyl formate,(lR,3R,5R,7R), I16 1,6,6,IO-Tetramethyl-3,11dioxatricyclo[5.4.0.02~4]undecane, 380 3,4,7,1 I-Tetramethyl-I,3,6,lOdodecatetraene,(3Z,6E,3E),277

Thaurnetopoea pityocattipa, 64 Thyridopteryx epherneraefortnis, 10I Tiger moth(s), 8, 66 Tobacco budworm, 133 Tobacco stem borer, 23 Toxorrypana curvicauda, 482 Triboliuni castaneutn, 141 Triboliutn cotifisutn, 14 1 Triboliumfreetnani, 14 I Trichoplusia n i , 26 4,7-Tridecadienyl acetate,(4E,7Z), 68 3-Tridecenyl acetate,@), 23 3,3,7-Trimethyl-2,9dioxatricyclo[3.3. I .04.’]nonane, 436 3,7, I I-Trimethyl-1,3,6,10dodecatetraene,(3E,3Z,6E),273 3,7,1 I-Trimethyl-2,4,6,10dodecatetraene,(2Z,42,62),276 3,7,1 I-Trimethyldodeca-2,6,10trienal,(ZE,6E), 336 3,7,1 l-Trimethyldodeca-2,6,10trienal,(22,6E), 336 15,19,23-Trimethylheptatriacotane, 13 6,10,13-Trimethyl-l-tetradecanol, 128 I ,2,6-Trimethyltetradecyl acetate, 122 I ,2,6-Trimethyltetradecyl propanoate, 122 24-Tritriaconten-2-one,(Z),175 Trogodermal,(R,E), I52 Trogodermal,(R,Z), 152 Trogodertna glabrum, 2 16 Trogodertna gratiariutn, 152, 2 16 Trogoderma species, 152 Trypodendron lineatutn, 435, 436 Tsetse fly, 12, 13 Turnip moth, 25 Tyrophagiis pictrescenriae, 29 I

Ulretheisa ornatrix, 66, 83 7, IO-Undecadien-4-olide,(E),233 5-Undecenoic acid,(Z,E), 210 1,3,7,7-Tetramethyl-2-oxabicyclo[4.4.0]dec-9-6-Undecen-2-01,(2), I 1 I en-S-one,(lR*,3S*,6R*), 380 5-Undecen-2-one,(Z), 157 3,4,7, I l-TetramethyI-6,lOtridecadienal,(3S,4R,6E,IOZ), 148 4,6,10,12-Tetramethyl-2,4-trideradien-7- Varied carpet beetle, 210 one,(2E,4E), 184 Velvetbean caterpillar moth, 82 Tetramoriurn iwipuruni, 10 I Vespa orientalis, 242 Thamnophis sirtalis parietalis, 175 Vetch aphid, 364 Thaumetopoea processionea, 63 Viraceapolistiforttiis, 74

531

532

Subject Index

Wax moth, 138 Western balsam bark beetle, 394 Western corn rootworm, 113 Western pine beetle, 381, 394 Western tent caterpillar, 131 White peach scale, 330 White pine sawfly, 128 Wild silk moth, 70 Winter moth, 81

Xylocopa hirsutissima, 220 Xylorrechus pyrrhoderus, 109, 19 I

Yellow mealworm, 1 1 1 Yellow peach moth, 133 Yellow scale, 326 Zeuzera pyrina, 14

The Total Synthesis of Natural Products, Volume9 Edited by John ApSlmon Copyright © 1992 by John Wiley & Sons, Inc.

Fomula Index

533

534

Formula Index