Compendium of Organic Synthetic Methods
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Compendium of Organic Synthetic Methods
Compendium of Organic Synthetic Methods Volume 6 MICHAEL B. SMITH DEPARTMENT OF CHEMISTRY UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT
A Wiley-Interscience Publication
JOHN WILEY & SONS New York
0
Chichester
e
Brisbane
0
Toronto
0
Singapore
A NOTE TO THE READER
This book has been electronically reproduced from digital information stored at John Wiley & Sons, Inc. We are pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.
Copyright @ 1988 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Catalog Card Number: 71-162800 ISBN 0-471-84896-4 1 0 9 8 7 6 5
PREFACE It has been sixteen years since Ian and Shuyen Harrison first published the Compendium of Organic Synthetic Methods to facilitate the search for functional group transformations in the formidable body of the original literature. In Volume 2 this concept was expanded to include difunctional compounds. Louis Hegedus and Leroy Wade carried on this important compilation in Volume 3 and Wade continued with Volumes 4 and 5. Volume 6 is intended to continue the Harrisons’ stated purpose of “a comprehensive one-volume listing of synthetic methods as an intermediary between the chemist and the literature.” Compendium of Organic Synthetic Methods, Volume 6, presents the functional group transformations and difunctional compound preparations of 1983, 1984, 1985, and 1986. The classification schemes of the first five volumes have been followed but a new chapter has been added. Each literature citation now includes all authors and the text concludes with an Author Index. The new Chapter 15 classifies the oxides of nitrogen, sulfur, and selenium with section headings identical to Chapters 1-14. The difunctional compounds now appear in Chapter 16. The experienced user of the Compendium will require no special instructions for the use of the new oxides chapter or the complete volume. Author citations and the Author Index have been included to facilitate literature searches and to follow the current work of a particular author. The citations should not prove obtrusive and will hopefully assist the synthetic community . I wish to express my gratitude to Professor Michael Edwards who first suggested this project to me. I also wish to thank Professor Leon Ghosez who provided the facilities for a pleasant sabbatical leave, which allowed completion of the research for this text. My thanks to Tae Woo Kwon, Jennline Sheu, Royce Menezes, Chung Jen Wang, Paul Keusenkothen, and Young Chan Son who proofread parts of the manuscript and offered many helpful suggestions. I want to thank my wife Sarah and son Steven for their patience and moral support throughout this work.
MICHAELB. SMITH Storrs, Connecticut June 1987 V
CONTENTS ABBR EVIAT1ONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION 1 PREPARATION OF 2 PREPARATION OF AND ANHYDRIDES 3 PREPARATION OF 4 PREPARATION OF 5 PREPARATION OF 6 PREPARATION (2F 7 PREPARATION OF 8 PREPARATION OF 9 PREPARATION OF THIOETHERS 10 PREPARATION OF 11 PREPARATION OF 12 PREPARATION OF 13 PREPARATION OF 14 PREPARATION OF 15 PREPARATION OF 16 PREPARATION OF AUTHOR INDEX
ACETYLENES CARBOXYLIC ACIDS, ACID HALIDES, ALCOHOLS, PHENOLS, AND THIOLS ALDEHYDES ALKYLS, METHYLENES, AND ARYLS AMIDES AMINES ESTERS ETHERS, EPOXIDES, AND HALIDES AND SULFONATES HYDRIDES KETONES NITRILES OLEFINS OXIDES DIFUNCTIONAL COMPOUNDS
ix xiii xiv xv 1 8 19 51 67 98 113 139 164 181 194 205 239 248 272 280 493
vii
ABB R EVIAT1ONS 0 Ac acac AlBN aq.
-a
9-BBN Bn (Bz)
ii
Acetyl = -CCH, Acetylacetonate Azo-bis-isobutyronitrile Aqueous 9-Borabicyclo[3.3.1Inonylboryl 9-Borabicycio[3.3.1.]nonane Benzyl = -CH,Ph
0
I/
cat.
t-Butoxycarbonyl = -C-CB -tu 2,2'-Bipyridyl n-BUtyl = -CHzCH,CHzCH3 Carboxamidomethyl Cerric ammonium nitrate = (NH,),Ce(NO,), CycloCatalytic
CBZ COD CP CY DABCO dba DBE DBN DBU DCC DCE DDQ DEA DEAD Dibal-H Diphos-4 DMAP DME
Carbobenzoxy = -COCH,Ph 1,5-CycIooctadienyl Cyclopentadienyl Cyclohexyl 1,4-Diazabicycl0[2.2.2]octane Dibenzylidene acetone 1,2-Dibromoethane = BrCH,CH,Br 1,8-Diazabicyclo[5.4.O]undec-7-ene 1,5-Diazabicycl0[4.3.O]non-5-ene 1,3-Dicyclohexylcarbodiimide = C,H13-N=C=N-C,H13 1,2-DichIoroethane = CICH,CH,CI 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone Diethylamine = HN(CH,CH,), Diethylazodicarboxylate Diisobutylaluminum hydride 1,4-bis-(DiphenyIphosphino)butane 4-Dimethylaminopyridine Dimethoxvethane
DMF
N,N-Dimethylformamide
Boc bPY WPY) Bu CAM CAN C-
0
I/
=
HCNMe,
ix
ABBREVIATIONS
X
dPPe dPPf dPPP dvb eee EE Et EDA EDTA FMN fod FP FVP hv
1,5-HD HMPA HMPT iPr LlCA LDA LTMP mcpba Me MEM MOM Ms MTM NAD NADP NBD NBS NCS PCC PDC PEG Ph Pip Pr PY quant. Red-Al TBAF TBHP
1,2-bis-DiphenyIphosphinoethane bis-(Dipheny1phosphine)ferrocene 1,3-bis-(Diphenylphospine)propane Divinylbenzene Electrolysis Enantiomeric excess Ethoxyethyl Ethyl = -CH,CH, Ethylenediamine = H,NCH,CH,NH, Ethylenediaminetetraacetic acid Flavin mononucleotide tris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate Cyclopentadienylbiscarbonyliron Flash vacuum pyrolysis Irradiation with light 1,5-Hexadienyl Hexamethylphosphoramide = (Me,N),P=O Hexamethylphosphorous triamide = (Me,N),P lsopropyl = -CH(CH,), Lithium cyclohexylisopropylamide Lithium diisopropylamide = LiN(iPr), Lithium 2,2,6,64etramethylpiperidide mefa-Chloroperoxybenzoic acid Methyl = - C H , p-Methoxyethoxymethyl = MeOCH,CH,OCH,Methoxymethyl = MeOCH,Methanesulfonyl = CH3SO2-Methylthiomethyl = CH3SCH2Nicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Norbornadiene N-Bromosuccinimide N-Chlorosuccinimide Raney nickel Polymeric backbone Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol Phenyl = -C,H, PiDeridine = H&CH,CH,CH,CH,.’ . . . n-Propyl = -CH2CH2CH3 Pyridine = C,H,N Quantitative yield [(MeOCH,CH,O),AIH,]Na n-Bu,N+Ff-Butylhydroperoxide = Me,COOH
ABBREVIATIONS
TEMPO TFA TFAA Tf THF THP TMEDA TMS TMP To1 Tr TRlS Ts (Tos)
tBu
f-BUtyl = --C(CH3)3 Tetramethylpiperidinyloxyfree radical Trifluoroacetic acid = CF,COOH Trifluoroacetic anhydride = CF,COCCH, Triflate = -OSO,CF, Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine Trimethylsilyl = -Si(CH,), 2,2,6,6-Tetrarnethylpiperidine Tolyl = 4-CeHdCH3 Trityl = --CPh, Triisopropylphenylsulfonyl Tosyl = p-toluenesulfonyl
NN
Sonication
xi
I N0113310Hd I
szz
6LZ
8LZ LZZ
SLZ 61Z PLZ L LZ
ELZ SLZ
ZLZ E1Z
OLZ OLZ L9Z 602 L9Z 80Z P9Z LOZ E9Z 9OZ 092
soz
892 POZ LSZ EOZ
9SZ
ooz ESZ 661 ZSZ 861 192 L6 1 8PZ 961
9PZ S ~
SPZ €61 SPZ z6t PPZ 161 EPZ 061
IPZ 981 6EZ
P81
6EZ 181
EEZ L 081 LEZ 6L1 1EZ 8L1 EZZ ut ZZZ 9Ll OZZ SLL 61Z PLL 81Z EL1 L1Z ZLl L1Z LLL 9 LZ OL 1 S1Z 691 60Z 891 902 L91 SOZ 991
POZ sgt
EOZ E91 EOZ zgt
002 091 661 6Sl 861 8S1 861 LSL
L61 PSl S61 ESL P61 ZSL
261
ost Z61 6Pl 161 LPL 06 1 9 t1 881
stc
L81
PPl
L81
ZP1 981 OP1 S81 6El 181 8El 181 LEL
6L1 SEL SL1
PEL EL1 ZEL
1LL OEL OL1 6Z1 691 8ZL 69L LZL
891 SZ1 L91 tZ1 S91 EZL
S91 1Zl
291 ozt 191 611 091 811 8S1 LLL 8S1 911 SSL
sit
Ell
PS1 tll 6Pl
6tl Z11 8P1 111 8P1 011 9P1 601 EPL 801 opt LO1 6E1 901
sot
ZEL ZEl to1 LEL E01 8Z1 ZOL 8Z1 101 SZ1 001
SZ1 86 L11 L6 Ell
111 06
011 68 601 88 801 ~8
se
LO1
901 E8 PO1 Z8 101 18
001 6L
96 S11
S6 PI1 P6
86 LL
Ell
E6 ELL 26
89
L6 SL 18 PL 08 EL 6L ZL LL LL 1L OL 1L 69 69
69 s9 89
W
89 E9 LS Z9 L9 L9
€9 09 Z9 6s
ss
19 LS 19 9s 6S 6S
tG
86 ES 8S ZS
LS 0s 9S 6P 29 8P 1s LP
SP
SP
EP
PP
SE
zt
EE op
8E
6Z 6E 82
LZ 9E 92 SE 12
PE
02
EE 61 ZE 61 1E
91
OE
sz
91 6Z S1 82 PI LZ Pl 92 Zl
11 EZ 11
zz
01
oz
6 61
8 L1 8 91
L st 9 tl
S
zc
S 01
P 8
spunodluo3snoaueiia3siyy
SWalO
SallJJlN
sawax
(HH) S~PIJPAH
saiews 'saieuojlns 'saplieti
sapixoda 'sJaqI3
sJais3
saulluy
sap!wv
z
P
slouaqd 'sloyoqv sapwAuue 'saplieu p i x SPl3e 311AXOqJe3
SaPAWPIV
slhe 'saualAqiaw 'slAylv
Z
saualAia3v
E
1 1
SaNflOdWO3 lVNOll3NfldONOW 'XXINI
._ .-
318
305
322
340
357
341
355
354
339
351
336
351
335
371
349
368 348 370
366
347
361 344 362
343
374
387
356
385
355
381
381
354
376
351
350
361
410
362
409
400 360 401
357
392
436
367
435
366
429
365
427
453
371
452
370
448
446 369
464
374
463
373
372
458
481
481
376
375
Blanks in the table correspond to sections for which no additional examples were found in the literature.
289
311
332
340
305
331
302
288 321
329 330 332
301
309
320
327
299
317
313
296
326
325
315 316
307
292
287
285
305
282
Sections-heavy type Pages-light type
484
377
INDEX, DIFUNCTIONAL COMPOUNDS
INTRODUCTION Relationship between Volume 6 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 6 presents about 1 100 examples of published methods for the preparation of monofunctional compounds, updating the 7000 in Volumes 1 through 5. In addition, Volume 6 contains about 900 examples of preparations of difunctional compounds and various functional groups, updating the sections introduced in Volume 2. For Chapters 1 through 14 the same systems of section and chapter numbering are used as in previous volumes. Chapter 15 is new and classifies the preparation of oxides of nitrogen (nitro compounds, nitrones, N-oxides, etc.), sulfur (sulfoxides and sulfones), and selenium (selenoxides and Se dioxides) according to the scheme used for all other monofunctional compounds. Therefore, “Oxides from Acetylenes” appears as Section 21 1 and the chapter concludes with “Oxides from Miscellaneous Compounds”, Section 225. The difunctional compounds now appear in Chapter 16 (Chapter 15 in Volumes 2 through 5) but the section numbers remain the same. A minor change from previous volumes is the inclusion of thiols with all alcohol classifications and sulfides (thioethers) are classified with ethers. Both of these changes are reflected in the chapter titles, section titles, and citations. These changes do not alter the fundamental organization. Each literature citation follows the notation used in previous volumes but is accompanied by a complete author list. The principal author(s) are denoted by an asterisk (*). Following Chapter 16 is an alphabetical listing of all authors (last name, initials). Classification and Organization of Reactions Forming Monofunctional Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in ascending order of year cited (1983-1 986), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases xv
xvi
INTRODUCTION
in the length of carbon chains; for example, the reactions t-BuOH + t-BuCOOH, PhCH20H + PhCOOH, and PhCH=CHCH20H + PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated ketones, aldehydes, esters, acids, and nitriles have been placed in category 74 (alkyls from olefins). The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H + RCH,COOH (carboxylic acids from hydrides), RMe + RCOOH (carboxylic acids from alkyls), RPh + RCOOH (carboxylic acids from aryls). Note the distinction between R2C0+ R2CH2(methylenes from ketones) and RCOR’ + RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (alkyls, methylenes, and aryls from olefins). The following examples illustrate the classification of some potentially confusing cases: RCH=CHCOOH + RCH=CH2 RCH=CH2 + RCH=CHCOOH ArH + ArCOOH ArH --j ArOAc RCHO + RH RCH=CHCHO + RCH=CH2 RCHO --j RCH, R&H, + RZCO RCH,COR + R,CHCOR RCH=CH2 -+ RCH,CH, RBr CH CH + RC=CR
+
ROH
+
RCOOH-,
RCH=CHCHO RCH=CHCN
+
RCOOR RCH&H&HO
+ RCH,CH,CN
Hydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from methylenes Ketones from ketones Alkyls from olefins Acetylenes from halides; also acetylenes from acetylenes Esters from alcohols; also esters from carboxylic acids Alkyls from olefins Alkyls from olefins
How to Use the Book to Locate Examples of the Preparation or Protection of Monofunctional Compounds. Examples of the preparation of one functional group from another are located via the monofunctional index on p. xiii, which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes; Section 2, acetylenes from carboxylic acids; and so forth. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of the index. Thus Section 1 gives examples of
INTRODUCTION
xvii
the reactions of acetylenes that form acetylenes; Section 16, reactions of acetylenes that form carboxylic acids; and Section 31, reactions of acetylenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1, 17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of acetylenes from acetylenes; carboxylic acids from carboxylic acids; and alcohols, rhiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74 (alkyls, methylenes, and aryls from olefins). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance is in Section 199 (olefins from aldehydes) and Section 207 (olefins from ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (alcohol, thiol-aldehyde) and in Section 330 (alcohol, thiol-ketone). Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and olefins are also indexed on p. xiii. The pairs of functional groups alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should, of course, also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In no instance should the citation be taken as a complete experimental procedure. Not to refer to the original literature could be hazardous. The original papers usually yield a further set of references to previous work. Subsequent publications can be found by consulting the Science Citation Index.
Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions
xviii
INTRODUCTION
of the groups do not affect the classification. Thus preparations of 1,2aminoalcohols, 1,3-aminoalcohols, and 1,4-aminoaIcohok are included in a single section. Difunctional compounds that have an oxide as the second group are found in the monofunctional sections for the nonoxide functional group. Therefore, the nitroketone product of oxidation of a nitroalcohol is found in Section 168 (ketones from alcohols and thiols). Conversion of an oxide to another functional group is generally found in the “Miscellaneous” section, so conversion of a nitroalkane to an amine is found in Section 105 (amines from miscellaneous compounds). The following examples illustrate the application of this classification system: Difunctional Product RCEC-C~CR RCH(0H)COOH RCH=CHOMe RCHF, RCH(Br)CH,F RCH(OAc)CH,OH RCH(OH)CO,Me RCH=CHCH,CO,Me RCH=CHOAc RCH(OMe)CH,SO,CH,CH,OH
Section Title Acetyleneacetylene Carboxylic acid-alcohol Ether-olef in Halide-halide Halide-halide Alcohokster Alcohokster Ester-olefin Ester-olefin Alcohol-ether
How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xiv gives the section and page corresponding to each difunctional product. Thus Section 327 (alcohol, thiol-ester) contains examples of the preparation of hydroxyesters; Section 323 (alcohol, thiol-alcohol, thiol) contains examples of the preparation of diols. Some preparations of olefinic and acetylenic compounds from olefinic and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, RCH=CHBr + RCH=CHCOOH, carboxylic acids from halides (Section 25, monofunctional compounds) or carboxylic acid-olefin (Section 322, difunctional compounds). In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctionalcompounds. Thus the reaction RCI + ROH can be extended to the preparation of diols by using the corre-
INTRODUCTION
xix
sponding dichloro compound as a starting material. Such methods are not fully covered in the difunctional sections. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. Compounds of the type RCH(OAc)CH,OAc (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH,OH (alcohol-alcohol),
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 1 PREPARATION OF ACETYLENES
SECTION 1 : Acetylenes frau Acetylenes 1.
2-iodothiophene Pd[PPh3I4,
HC sC-C-OH
BnEt3NC1/OH-/RT
I
CH3
2.
PhBr,
C o
CuI
80°C,
* Ph-C
50 h
Carpita, A . ; Lessi, A . ; Rossi, R.
*
80%
Synthesis, (19841, 571
[PPh3I2PdXI2 Ph-CECH
t
Ph-X
t Ph-CSC-Ph NEt3
CHC13-CuI;
X = I; X '
Bunagin, N.A.; DMF;
X = Tf;
Chen, Q-Y. Ph, Ph'
C=C=O
1.
97%
Ponomarev, A.B.; Beletskaya, I . P . M l Acad Sci USSR, (19841,
----
X'
* ; Yang, t
= Ph,
= C1,
Z-Y.
2,1171
Tetrahedron Lett, (1986), 5% Pd[PPh3I4 THF,
1433
91 %
C1
HCEC-nPr
33,
Ph2CHC
C-EPr
120°C 81 %
Mitsudo, T.; Kadokura, M.;
*
Watanabe, Y . Tetrahedron Lett, ( 1 985),
26,
3697
2
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 1
2 LBu-Cl A1 C1
Me3Si-CsC-SiMe3
iH2C12,
* ; Ottana, R.;
Capozzi, G.
n B u - C =CH
Rcineo, G.; Marcuzzi, F.
Gazz Chim Ital, ---
R = Brown,
<4\
* C.A. ; Desai,
-CL ,,,,,
5 7 7;
THF-Et20 15 min _?C1 O H 2 5 C S C C H 2 0 T H P
0- R T , 3 h
DFISO,
HOH
* Chong, J.M. ; Wong, S.
84%
Tetrahedron L e t t , (19861,
1. LiCsCC H 4 9' OMe
Et
Me
2 . "C10H25Br
2.
nB u - C S C -
/
M.C.; J a d h a v , P . K . J Org Chem, (1986), 51, 162 --O"C,
3. 4.
115,31 1
(95%ee,R)
1. MeLi, HCECCH20THP
t
.Et R2B-C P H Me NaOH/H202
4.
( 1985) ,
RT
12, -78°C
3.
tBU-CsC-LBu
70%
1. nBuLi, 2.
*
-17°C
0°C
I2
3. ox.
*
3, 5445
C8H1 7C % C C 4 H 9
75%
S i k o r s k i , J.A.; Bhat, N.G.; Cole, T.E.;
Wang, K.K.; Brown, H.C.
J Org Chem, (19861, 51, 4521 ---
*
SECTION
3
A C E T Y L E N E S FROM A L D E H Y D E S
SECTION 4
2: Acetylenes -f m Acid Derivatives 1 . Li/Hg,
0 II Ph-C-C1
THF t
2. Li/Hg
Ph-C =C-Ph
51 %
*
-Chem Ber,
Homer, L. ; Dickerhof, K .
(1983), 116, 1615
1. 2 IBuLi 2 Ph3PEt
+
Br
-
2. EtC-C1
1
______j
3. FVP ( 7 5 0 ° C )
Aitken, R . A .
* ; Atherton,
J.I.
Et-CsC-Et 8 0 7:
JCS Chem C a m , ---
(1985), 1140
SECTION 3: Acetylenes f m Alcohols and Thiols
No Additional Examples SECTION 4: Acetylenes
from
Aldehydes
1. nBuLi, THF, -78°C 2. PhCHO PhCH2S02Ph
3. Ac20-Py
4. tBuOK/THF
b
P h - C I C-Ph 86%
Mandai, T,; Yanagi, T . ; A r a k i , K . ; Morisaki, Y . ; Kawada, M.; Otera, J. J Am Chem Soc, (1984) , 106,3670 ----
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
4
SECTION 8
5: Acetylenes from Alkyl, Methylenes, and Aryls SECTION No Additional Examples SECTION 6: Acetylenes from Amides
No Additional Examples SECTION 7: Acetylenes from Amines
No Additional Examples SECTION 8: Acetylenes from Esters
AcOy'%/Ph
H C n C CH cat.
Br
Pd[PPh3I4,
*
CH2Ph
I
, 42ti
* THF
Br
J Org Chem, (19831, 3,5302
Keinan, E. , Peretz, M. 1.
HCECCH2
S nnBu
CH2Br2, T H F -78°C
CH2C02Et 2 . (iPr)2SiC1
* Kowalski, C.J. , Lal, G.S., Haque, M.S.
J Am Chem Soc, ----
*
80%
CH2Ph
I
CH,CaCOSi ( i Pr)3 6 6 7;
(19861, 108,7127
SECTION 1 2
5
A C E T Y L E N E S FROM KETONES
SECTION 9: Acetylenes fmm Ethers, Epoxides,
and Thioethers
No Additional Examples
from Halides and S u l f O M t e s
SECTION 10: Acetylmes
2 Ph2P-Li
*
P hCH- C H 2 B r
I
Ph-C
TH F
Br
71 %
*
Gillespie, D.G.; Walker, B . J .
SECTION 1 1 : Acetylenes
CH
--JCS Perkin I, (1983), 1689
fmm Hydrides
No Additional Examples
For examples of the reaction RClCH 300 (Acetylene - Acetylene)
-*
RC~C-CICR' see section
SECTION 12: Acetylenes fmm Ketones 1. PhSeBr 2.
0
210oc
I1
2 Ph3P=CHCPh
3. nBuLi/THF
4.
Braga, A.L.;
*
Ph-CEC-CH3
CH31
*
45% o v e r a l l
Ccinasseto, J . V . ; Petragnani, N. Synthesis, ( 1 984), 240
6
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . LDA,
0I I Ph-C-CH3
Negishi
,
THF
0
2.
C1P(OEt)2
3.
2.25
4.
HOH
P
LDA
Ph-CSCH
80%
*
E. ; King, A.O.:
SECTION 13: Acetylenes
SECTION 1 4
Tour, J.M.
Org Syn, (1985) ,
64,44
from Nitriles
No Additional Examples SECTION 14: Acetylenes
fnrn Olefins
Pd[OAcI2*OPTA CH3CH2CH=CHnBu
+
aa. EtOH, 70°C
Et-C=C-fiBu
OPTA = o l i g o - p - p h e n y l e n e t e r e p h t h a l a m i d e 3c
C u m , G . ; Gallo, R . ;
Ipasli, S . ; Spadaro, A. JCS Chem Caun, ( 1 9851, 1571 ---
1. 2 nBuLi CH2=C=CH2
*
2,
98%
HOH
HOOZ, J. ; Calzada, J . G . ;
*
C 7 H 1 5 CH 2 - C = C H
McMaster, D. Tetrahedron Lett, (1985),
88%
26,
271
SECTION 15
7
P R O T E C T I O N OF A C E T Y L E N E S
NaN02,
AcOH
Me2C=CH(CH2),4CH3
CH3 ( C H 2 ) , 4C S C C H 3 0
-
60°C 67%
SECTION
15: Acetylenes fran Miscellaneous
N-NH2
II
C u ( OAc )
Ph-C-C-Ph
IIN - N H ,
0 2 - C H 2 C 1 2 : Py
L
CanpomdS
*
Ph-C E C - P h 97%
*
T s u j i , J. ; Kezuka, H . ; Toshida, Y . ; Takayanagi, H.;
K.
Tetrahedron, (1983),
SECTION 15A: Protection
of
Acetylenes
No Additional Examples
Yamamoto,
3,3279
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES
SECTION 16: Acid Derivatives from Acetylenes 1 . "BuLi, 2. 2C6Hl1-CECH
THF
PhSSPh
+
3 . HOH
n C 6 H 1 CH2C02H
4. HgS04, H2SQ4
Abrams, S.R.
*
67%
AcOH Can J ---
Chem, (19831, 61, 2423
SECTION 17: Acid Derivatives -from Acid Derivatives c1
t
I
Me2N-C=NMe2 C12 PhC02H NEt3,
-30'
+
*
0 It PhC-)20
0°C
88%
Fujisawa, T.*; Tajima, K.: Sato, T.
--WiLl Chan Soc Jpn, ( 1 983), 56,
0
bL
1 . KOTMS, 2.
KQTMS
0
Et2Q b
PhCCl
* Laganis, E.D. ; Chenard, B.L.
3529
Ph:O-K+
(anhydrous)
Tetrahedron Lett, (19841, 25, 5831
SECTION 19
9
A C I D S FROM ALDEHYDES
25°C
*
Kobayashi , Y. : Itabashi , K.
90%
*
Synthesis, (1985), 671
SECTION 18: Acid Derivatives from Alcohols -and Thiols
No Additional Examples Acid Derivatives from Aldehydes SECTION 19: -
-
SPh
I
Cr03
nC, 4 H 2 5 - C H
I
-
H2S04
*
"'14
H 2 9 CO 2 H
0°C
OMe
78%
*
Mandai, T.; Hara, K.; Nakajima, T.: Kawada, M.; Otera, J. Tetrahedron Lett, ( 1 9831, 2, 4993 1 . LDA,
/CHzCrnN
THF,
TMS-C1
0°C
Ph-N \
2 . "PrCHO,
CH3
3.
*
10% aq.
0°C
*
nPrCH2C02H -
THF
Takahashi, K. : Shibasaki, K.; Agura, K.: Iida, H. J Org Chem, (19831, 3, 3566
44%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
10
1
.
NaCl 02-H202, aq.
CH3CN,
7 dpcH N a H 2 P 0 4
“3
Na2S03
*
Dalcanale, E. ; Mantanari, F.
k!
H cH 2 < ~
04-
* -J Org Chem,
1 CH2Ph CH,CHO
88%
(1986),
.
51, 567
0
!
ti 0 CH 2<
05-
‘
5% NaH2P04
Abiko, A.; Roberts, J.C.;
C02H
a q . HC1
tBuOH
\
I
3.
nC H - 3 7 \ / p
*
KMn04, 1 0 rnin
0
SECTION 20
* Takemasa, T.; Masamune, S.
-
T e t r a e o n Lett, (1986) ,
98%
3, 4537
T r C l 0 4 , LBuOOTFlS CH2C12,
-45°C
2. p i p e r i d i n e , 3 . a q . HC1
HOH,
90°C
>
CH2Ph
I
CH2C02H
73%
Mukaiyama, T.; Miyoshi, N.; Kato, J.; O h s h i m a , M . Chem Lett, (1986), 1385 -Related methods: Carboxylic Acids from Ketones (Section 27) Also via: Esters (Section 109) SECTION 20: Acid Derivatives from Alkyl, Methylenes, and Aryls
Chakraborti , A.K.; Ghatak, U.R.
*
--JCS Perkin I, (1985) , 2605
A C I D S FROM ESTERS
SECTION 23
$
Ru04
3 NaOCl,
pH 9 ,
Bu4NBr,
Q
C02-Nat
25OC
C1CH2CH2C1
*
c1
c1 Sasson, Y.
11
* ; Zami, __ .
G.D.;
Neumann, R .
.J
--Org
Ch&,
*
84%
(1986), 51, 2880
SECTION 21: Acid Derivatives -from Amides
No Additional Examples SECTION 22: Acid Derivatives from Amines
-
t
cat. PhH,
CO,
C O ~ ( C O ) ~> aq.
NaOH
65OC,
hv
+OoH \
8 5% Y
Brunet, J . J . ; S i d o t , C . ; Caubere, P . --J Org Chem, (19831,
9, 1919
SECTION 23: Acid Derivatives -Prom Esters
MeSiC13, Me C HC 0 Me Olah, G . A .
Y
NaI
>
Me CHC 0 H
CH3CNJ r e f 1ux
; Husain, A . ; Singh, B . P . ; Mehrota, A . K . J Org Chem, (19831, 48, 3667 ---
70%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
12
0 II
e
SECTION 25
-
P t electrodes Bu4NBr,
aq.
CH3CN 94%
Kimura, M.; Matsubara, S.; Sawaki, Y. --JCS Chem Cam, (1984), 1619 0 II P hCOCH2CH =C t i 2
Te/NaBH4 EtOH,
AcOH,
2h
0 II PhCOH
*
r e f 1ux
*
Shobara, N.; Shanmugam, P.
95%
Ind J Chem B, (1986),
z, 658
Other reactions useful for the hydrolysis of esters may be found in Section 30A (Protection of Carboxylic Acids). SECTION
3: Acid
Derivatives from Ethers, Epoxides, Thioethers
and
No Additional Examples SECTION 25: Acid Derivatives from Halides c1
/
t_BuOH
CH2=C
\
c1
and SulfOMteS
+
t_BuCH2C02H
a q . H 2 S 0 4 , 2°C
* Randriamahefa, S.; Deschamps, P.; Gallo, R.
Synthesis, ( 1 985), 493
90%
SECTION 25
A C I D S FROM H A L I D E S
1 atm CO
M(CO),, PhCH
\
aq.
13
P
*
Ph-CH-C02H
Br
benzene;
R=H;
M=Fe;
n=5
*
7 5%
Tanguay, G.; Weinberger, B.; des Abbayes, H. Tetrahedron E ,(19831, EtOH/NaOH;
R=Me;
M=Co;
n=4
80%
Francalanci, F.; Gardano, A.; Foa, M. J Organomet Chem, (1985),
-
Bu4NC1 O 4 Sock, 0.; Troupel, M.;
cat. PhI
282,
277
78%
Perichon,,J. Tetrahedron Lett, (19851,
-
Pd[PPh3I4,
2, 4005
26, 1509
PPh3
e-,
Pt electrode
DMF,
E t 4 N O T s , C02
w
PhC02-Kt 92%
Torii, S.*; Tanaka, H.; Hamatani, T.; Morisaki, K.; Jutand, A . ; Pfluger, F.; Fauvarque, J.-F. C h a o Lett, (19861, 169
--
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
14
Q
1. LBuLi,
Br
2.
SO2,
THF,
3.
Q
-60°C
so2c1
-60°C ~
SECTION 27
--
S02C1 2/hexane
9 5%
OMe
0M e
Yonemitsu, 0.
Hanada, T.*;
Synthesis, (1986), 852
SECTION 26: Acid Derivatives from Hydrides
0”c5H11
n
COCl 2/Al C1 CH2C1
55%
Neubert, M.E.;
F i s h e l , D.L.
O r g z , (19831,
3,8
SECTION 27: Acid Derivatives from Ketones 0 II PhCCH2NEt2
1 0 30% H202 EtOH,
Wenkert,
* D. ; Eliasson,
$ \
t F u j i i , K.;
*
O°C
K.M.; R u d i s i l l , D. --JCS Chem C u m , (19831, 392
1 . HC(OMe)3,
PhC02H 8 9X
H30t
T1 ( N 0 3 ) 3 * 3 H 2 0
2. aq.
NaOH
3. aq.
HC1
Nakao, K.; Yamauchi, T.
89% t
Synthesis, (19831, 444
s
SECTION 28
ACIDS F R O M NITRILES
15
1 . Z n B r 2 , MeOH, R T 2 . 1 1 5 " C , 4h
*
6
0
H
3. OH-
*
48%
4. H +
Ciordano, C. ; Castaldi, G.; Uggeri, F.; Gurzoni, F. Synthesis, ( 1985) , 436 1 . KOAc, H O C H , C H , O H
e
Me0
o
a
3 . HC1
*
Synthesis, (1985), 505
1 . NaBr02/NaBr a q . NaOH, 0°C
Me2CHCH2CCH3
*
+ H30
2.
OH
80%
Castaldi, G. ; Ciordano, C.; Uggeri, F. 0 II
co
<
--L
Fe2CHCH2CO2H
95%
* Kajigaeshi, S. ; Nakagawa, T.;
Nagasaki, N.; Fujisaka, S. Synthesis, ( 1 985), 674
SECTION 28: Acid Derivatives
CH2Br
I
(CH2)3
I
CEN
''
from Nitriles
H O A o H , MeOH, H
2 . Mg, T H F
+ CH2C02H
i
*
(CH2)5
1
3 . CH3CH0 4 . a q . H2S04
Voss, C.; Gerlach, H.
* --Helv Chim Acta,
,CHCH3 HO
(1983),
37%
9,2294
16
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 ' *
-n C3 7H,
Giese,
C=N /
c=c,
CZ"
C C g H 1 3 NaBH4
H C
7\3
a q . CH2C12, 20°C
2 . a q . H2S04
* B. : Harnisch,
SECTION 30
/CHCH2c02H
+
45%
cC6H13
180°C H.;
Lachhein, S. Synthesis, (19831, 733
SECTION 29: Acid Derivatives from Olefins
A
1 . B H B r 2 . S M e 2 , CH2C1
2 . LiSCH2CH2SLi
3. L i C C 1 3 ,
Brown, H.C.
. aq. * ; 4Imai, T.
uC O O H
THF. -100°C
NaOH J Org Chem, (19841,
3,892
67%
a q . NaOH C1 2C=CHS02"Bu
H02CCH2S02~Bu 80%
Mirskova, A . N . ; Kryukova, Yu.1.; Levkovskaya, G.G.; S.A.: Voronkvo, M.G. -J Org Chem USSR, (19841,
--
Guseva,
M , 545
SECTION 30: Acid Derivatives from Miscellaneous Canpounds 1 . LiAlH.
4
CP
I
2 . CO/Ag'/THF 3. 4 BH3-THF
,F e, Me3 p"'
I
CO
"- c o
*
4. repeat 2-3, twice 5 . a q . Br,
Brown, S.L.; Davies, S.G.
*
JCS Chem Cam, ---
L
nBuC02H
42%
(19861, 84
SECTION 30A
OF A C I D S
PROTECTION
17
Review: "Synthesis of Dithiocarboxylic Aci ds"
Ramadas, S.R.: Srinivasan, P.S.; Ramachandran, J.; Sastry, V.V.S.K. Synthesis, ( 1 9831, 605 SECTION 3OA: Protection of Carboxylic Acid Derivatives
O C O O H
I
Boc
-
9 - f 1 u o r e n y l met h a n o l DCCy DMAP 6 0 % B'o c DEA
, RT
*
Kessler, H. ; Siegmeier, R. cI 0 2.
-
Me2CHCH
I t
NH3
*
(:>CH20Hy
-
A1
co2-cst
*
NH2
( NH4) 2Mo04 2 . HOH,
tl
CH2
0
1 . H202, 83%
Ph 8
---Angew Chem Int Ed x, (19831,
C1 CH2CNH2
/NHBoc
2,281
78%
Kunz, H. ; Waldmann, H.
\
Tetrahednxl Lett, (19831,
*
22,
/ NHBoc
\C 0 2 C H * C0IIN H
CH2
Martinez, J. ; Law, J.; Castro, B. Tetrahedron Lett, (1983),
85%
2,5219
62
18
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 30A
1 . S0Cl2 2. NEt,
HOCH~CH=CHCH~TMS 2% P d [ P P h 3 I 4 ,
Mastalerz, H.
CH2C12 90%
*
J Org Chem, (1984),
PET-OH, tBuOK
/COOH
*
DCC
85% /co2pET PhCH2CH
PhCH2CH
\
NHBoc
2, 4092
1 . 3 MeI, CH3CN f
2 . E t 2 N H , CH3CN PET = 2(2-pyridyl)ethyl
92%
\ NHBoc
*
Kessler, H. ; Becker, G . ; Kagler, H.; Wolff, M. Tetrahedron Lett, (1984), R
1 . NaH PhOCH(C1)Me
Eq
2.
*
R
3
COOH
0
5% T F A / C H 3 C N
95%
0
25, 3971
,j 0 TJ H 0 P h
O
c1
R = P h O C H 2 LII N H Alpegiani, M . ;
Bedeschi, A.;
Foglio, M . ;
Gazz Chim Ital, ---
Perrone, E. (1984), 114, 391
Other reactions useful f o r the protectio of carboxylic acids are included i n Section 107 (Esters from Carboxylic Acids and Acid Halides) and Section 23 (Carboxylic Acids from E s t e r s ) .
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 3 PREPARATION OF ALCOHOLS, PHENOLS, AND THIOLS
SECTION
31: Alcohols and
Thiols f m Acetylenes
Danheiser, R.L.*; Gee, S.K.
c
--aH J Org Chem, (19841,
CECH
C H 3 C E W CO)4Br
CICH
to1 u e n e
- 1 0"-RT
Sivavec, T.M.;
49,
1672
/
54%
10 m i n
* Katz, T.J.
OH
Tetrahedron Lett, (1985),
2,2159
SECTION 32: Alcohols and Thiols from Acid Derivatives
0
/I
CH3(CH2)4CC1
B3H8
nBu4N
+ B3H8 - , RT
MnCl 2 - 4 H 2 0 , T H F
*
octahydrotriborate * Tamblyn, W.H. ; Aquadro, R.E.; DeLuca, O . D . : Dao, T.V. =
TetrahedronLett
CH3(CH2)4CH20H 61:;
Weingold, D.H.;
, F 1 9 8 3 ) , 24, 4 9 5 3
20
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0 0 II II 1 . ClC-CCl/DMF CH3CN/THF, -3OOC
Br(CH2l5CO2H Fujisawa,
2.
* T. ; Mori,
0%-c1
N a B H 4 , -18°C
*
93%
T . ; S a t o , T.
Chem Lett, (1983), 835
CH20H
4
4.
2 . a q . HC1
Kotsuki,
Br( CH2)5CH20H
2 h
1 . Zn(BH4)2, T H F , 0°C T M E D A , 30 m i n
* H. ; Ushio,
SECTION 33
93%
Yoshimura, N.: Ochi, M. Tetrahedron E ,(19861,
Y.;
27, 4213
SECTION 33: Alcohols and Thiols from Alcohols and Thiols
, 2 & *
Ph
\
2 !BuLi,
HO&
OH
62%
\
*
-
Braun, M. ; Ringer, E.
CH O H , N i ( R ) CH3(CH2)8CH2CH20H
-
OH
Tetrahedron Lett, (1983), 24, 1233
3
200"C, 6 h 57 B a r
Sabadie, J.: Descotes, G.
*
FH 3 C H ~ ( C HI ~~ ~ H C H ~ O H 72%
Bull Chem Soc Fr, (1983), 11253
SECTION 34A
ALCOHOLS
FROM
21
ALDEHYDES
6
3
44%
*
---J Am Chem Soc, (19851,107, 2571
Posner, G.H. ; Canella, K.A. OH
1 0 % Pd-C,
CH30H
a q . NH40CH0
clQ1 Anwer, M.K.; Spatola, A.F.
\
10 m i n
qua n t
(1985),
Tetrahedron=,
26, 1381
SECTION 34: Alcohols --and Thiols from Aldehydes
The following reaction types are included in this section: A. Reductions of Aldehydes to Alcohols. B. Alkylation of Aldehydes, forming Alcohols. Coupling of Aldehydes to form Diols is found in Section 323 (Alcohol - Alcohol). Section 34A: Reductions
0 p h l i.- O C H 0
of Aldehydes
Alcohols
4 ;Bu~NBH(OAC)~
benzene,
Nutaitis, C.F.; Gribble, G.W.
*
80°C,
Id
*
0 Ph!OC .- F 1 2 0 H 884:
Tetrahedron Lett, (19831,2, 4287
-
22
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CHO
SECTION 34A
0 It Ph3SnOCH , 16OOC
> diglyme, 36 h 67%
Wuest, J.D.*: Zacharie, B.
B E R , E t O H , 25°C
CH3(CH2)4CH0 BER
=
J Org Chem, (1984),
3, 166
CH~(CH~)~CH~OH
5 h
99%
borohydride exchange resin
Yoon, N.M.*; Park, K.B.; Gyoung, Y.S. Tetrahedron Lett, (1983),
3,5367
R U C ~ ~ ( P P ~ T~H F) ~ ,
\
NEt3, HCOOH, RT
Khai, B.T.; Arcelli, A.
CH~(CH~)~CHO
-
Tetrahedron Lett, (19851,
Z n O C l 2.8H20
*
HOH, iPrOH, reflux 1 h
* Matsushita, H. : Ishiguro, S.; Ichinose, H.; Mizusaki, S.
-Chem Lett,
26, 3365
CH~(CH~)~CH~OH Izumi, A,;
(1985), 731
83%
SECTION 34B
23
ALCOHOLS FROM A L D E H Y D E S
31% H202,
cat.
G O M e
OH
CH30H
*
H2S04, RT 24 h
OoMe 94%
*
Matsumoto, M. ; Kobayashi, H.; Hotta, Y. --J Org Chem, (1984),3,4740 Review:
"cis-Alkyl and cis-Acylrhodium and Iridium Hydrides: M X l Intermediates in Homogeneous Catalysis"
*
Milstein, D.
Accts Chem Res, (19841,17,221 ---
Section 34B: Alkylation of Aldehydes, forming Alcohols
Aldol reactions are listed in : Section 324 ( Aldehyde-Alcohol and Section 330 (Ketone-Alcohol1. iPrCtiO,
TiC14
*
CH2C1
,/-HO
vPh 66%
(91% ee)
* Hayashi, T.; Konishi, M.; Kumada, M. J Org Chem, (1983), 48, -/
r
Ph
CHO
1. BnSiMe3, THF, 2.
H30'
TDAF 0 O C - v
281
HO r e f 1 ux/I\,Ph
+
r
Ph
85%
Bennetau, B.; Dunogues, J.
Tetrahedron Lett, (19831,3, 4217
24
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . PhCtiO,
9BBN -O T f
iFr2NEt
CH2C1 2/RT/1 7 h 2 . 30% h 2 0 2 / C H 3 0 H RT, 2h Hamana,
* H. ; Sugasawa,
SECTION 34B
78%
Chem Lett, (19831, 333
T.
OH
1 . B n B r , 2Sm12, T H F
nC7H1 5CH0
2 . 5 m i n , RT 2 . H30
t
I
*
nC7H1 5CHBn 86%
*
Souppe, J.: Danson, L.; Namy, J . L . : Kagan, H.B. J Organanet Chem, (19831, -
-
250, 227
1 . CH3CH2CH0 t
Cl
Hoffmann, R.W.
2. H2/Pt
* ; Landmann,
(76% ee)
5 0 7:
OH
[el
B.
Angew Chem Int Ed Engl, (19841, 23, 437
CH3Ti(OiPr)3,
n C 5 H 1 , CHO CH2C12,
15 h
OH
0°C
+
nC5H,
I
CHCH3 95%
Reetz, M.T.*: Westermann, J.: Steinbach, R.; Wenderoth, B.; Peter, R.; Ostarek, R.: Maus, S. Chem Eier, (19851, 1421 --
118,
SECTION 34B
ALCOHOLS
>
F R O M ALDEHYDES
25
nBuTi(OiPr)3, Et20
HIIIL\ CHO Ph
*
-33"- RT
P O H Ph ~ - B u
Ph *-Bu (88
12)
Reetz, M.T. * ; Steinbach, R.; Westermann, J.: Peter, R.: Wenderoth, B. Chem Ber, (1985), 118,1441
7 5%
--
(85% ee)
*
Seebach, D. ; Beck, A.K.; Roggo, S.; Wonnacott, A. -Chem Ber, (1985), 118,3673 MeTiC13,
OH
Et20
Reetz, M.T.
98%
* ; Kyung, S.H.;
Hullmann, M. Tetrahedron, (19861,
1 . PhCHO, T H F , -78"2.
% ',
PhCHCH3
2h
O'C,
/
I
>
PhCHO
9, 2931
24 h
RT
+
a q . NH4F
OH
I
PhCHCH3 78%
(85% ee)
*
Reetz, M.T. ; Kukenhohner, T.; Weinig, P.
Tetrahedmn Lett, ( 1 9861,
3, 571 1
26
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 35
CuBr.Me2S Me2S, E t 2 0 , - 3 0 ° C
1 . PhLi,
n
n
b
IL6'l 3
-
60"
* (97% ee, R ) Schreiber, S.L. ; Reagan, J. Tetrahedron Lett, (1986), 2, 2945
CH3(CH2)6CH0
BnC1,
e
- ,
DMF
OH
t
CH3(CH2)6CHBn
Mg a n o d e , s t a i n l e s s s t e e l c a t h o d e , 0°C Bu4BBr S i b i l l e , S.: d'Incan, E.; Leport, L.: Perichon, J. Tetrahedron Lett, ( 1 9861,
95%
2,31 29
Review: IIReactivity and Stereochemical Factors of the Reduction of Carbonyl Functions w i t h Metallic Borohydride" Caro, B . ; Boyer, B.; Lamaty, G . ; Jaouen, G. Bull Chem Soc Fr, (19831, I1281 ---Related Methods: Alcohols from Ketones (Section 42)
SECTION 35: Alcohols ---and Thiols from Alkyl, Methylenes, and -1.3
No examples of the reaction RR' + ROH ( R ' = a l k y l , a r y l , e t c . ) occur i n the l i t e r a t u r e . For reactions of the type RH + ROH (R = alkyl or a r y l ) see Section 41 (Alcohols and Phenols from Hydri des )
.
SECTION 36
27
ALCOHOLS FROM A M I D E S
1.
PdC12, NaOAc,
CuC12 N a C l , AcOH
2. M 0 0 ~ ( a c a c ) ~
tBuOOH
*
Jitsukawa, K.; Kaneda, K.; Teranishi, S. J Org Chemj (1983)j
99%
48,
389
SiMe(NEt2)2 1 . MgBr2
I
2 . 2 MeI,
C.H,(CH " 2 )4 ,CH
THF, L i
3.
OH
I
CuI
RT
CH3(CH2)4CHCH3
6N HC1
4 . 9 0 % H 2 0 2 , DMF KHF2, 60°C * Tmao, K. ; Iwahara, T.; Kanatani, R.: Kumada, M .
Tetrahedron Lett, ( 1 984) ,
25,
67%
1909 , 1913
SECTION 36: Alcohols and Thiols from Amides -
-
M e 2 N B H 3 Na THF,
t
66"C,
'OH
6h 96X
Hutchins, R.O.*C; NEt,
Learn, K.: El-Telbany, F.; Stercho, Y P. --J Org Chem, (1984) , 9, 2438 2.2 MeLi, -78°C -RT,
8h OMe
OMe
Sibi, M.P.;
OH
THF
* Snieckus, V.
Dankwardt, J.W.: J Org Chem, ( 1 986) , 51, 271 ---
9 0%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
28
SECTION 38
and Thiols from Amines SECTION 37: Alcohols ----
No Additional Examples
SECTION 38: Alcohols and Thiols from Esters
----
3 LiA1H4,
/c=N
Si02
\
C02Me
Kamitori, Y.;
CH2Ph
Et20,
Hojo,
reflux,
Cmins, D.L.
\:
CH3C
CH2
3h
.\
0.5
54%
R . ; Inoue, T.; Izumi, T. Tetrahedron E,(19831, 2,2575
LiBH4-2nBuMgC1
CH2Ph * h
THF,
r20°C,
* : Herrick,
i
CH2CHnBu
24h
I -
OH
J.J.
Tetrahedron Lett, ( 1 984), t
1. nBu4N NO3
- ( CH2) 5 C H 3
CH20H
* M . ; Masuda,
I
CH2C02Et
/ CzN
*
CH
-
1 0 % Pd-C
25, 1321
OH
I,,,,,H
benzene, 0.5h 2 . H2,
74%
~
H -( C H ~ ) 5~~ C
MeOH
6.0 %
(100% ee)
C a i n e l l i , C.: P l e s s i , L.
Manescalchi, F . ; Martelli, C.:
Panunzio, M.:
Tetrahedron E,( 1 9851,
26,
3369
SECTION 39
PhC1,
RT AcO
12h
AcO
Barton, D.H.R.
29
ALCOHOLS FROM ETHERS
* : Bridon, D.; Zard, S.Z. JCS Chem Cam, (19851, 1066 ---
35X
Related Methods: Carboxylic Acids from Esters (Section 23) Protection of Alcohols (Section 45A) Hydrolysis of Esters is covered in Section 23. SECTION 39: Alcohols ---and Thiols from Ethers, Epoxides, and Thioethers Additional examples of ether cleavages may be found in Section 45A (Protection of Alcohols and Phenols).
-&ovR
2.
R
:
HO
1. nBuLi +R /-
+ H30
Nl
1g'
0
Me
HI) +
' Y ' R Me
2)
(98
*
92%
Mikami, K.: Fujimoto, K.; Nakai, T. Tetrahedron Lett, (19831,24, 513
boMe b.. 3 Me2BBr, DCE
A
0°C + 2 5 ° C 3h
*
/k
75% * Cuindon, Y.*; Yoakim, C. ; Morton, H.E. Tetrahedron Lett, (1 983), 24, 2969
30
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 39
TiC14, CH2C12 -95°C
OH
5 5%
( Z : E = 4 :1 )
Tan, T.S.; Mather, A.N.;
Procter, G . ; Davidson, A.H. 585
JCS Chem Comn, ( 1 9841, ---
OH
3 nBuLi, THF
I
- ._ t
~ J C ~ H , ~ C H P ~
B F 3 * O E t 2 , -78°C 96% E i s , M.J.;
Wrobel, J . E . ;
0
1 . mcpba, C H 2 C 1 2
C02Me
2 . Ca(OH)2, RT
4. 3 . MeOH, T F A A , 4N 0E° tC3
SMe
Young, R.N.
)t
Ganem, B. ---J Am Chem Soc, (19841,
5. NH4C1
* ; Gauthier,
Yanaguchi, M .
k
-0 C02Me
SH
97 %
Coombs, W.
J.Y.;
Tetrahedron L e t t , (1984),
nBuLi,
CH 2CH P h
106,3693
-78
25, 1753
THF:HMPA
-
0°C
t
Ph
CH2CH20H 8 2 7;
( E :Z=8 :1 )
; Hirao, I .
Tetrahedron Lett, (1984),
3,4549
SECTION 39
R = gC6Hl1; R ' = H ;
Atsunori, M.: R = 1C8H17;
31
ALCOHOLS FROM ETHERS
TiC14,
Et3SiH,
-78°C
*
Ishihara, K.: Yamamoto, H. Tetrahedron Lett, (19861, R' = H
1 . MeMgBr 2.
PCC
3 . OH-
;
.-
Vankar, Y.D.*: Arya, P.S.; Rao, C.T. R
= 1C6Hl3;
.
2.
Barton, D.H.R.*:
Syn C m u n , (19831, NaHTe/EtOH/refl ux DBE
3.
Nickel boride
1 . BrCH2CH2-CH-CH
Li
2.
90 (89% ee)
25, 3947
96%(69:31)
9, 869 75% (1OO:O)
Fekih, A . ; Lusinchi, X. Tetrahedron L e t t , (19851,
Li I
3,987
x
*
Zn/CH C1 / M e 2 S i C 1 -2 . 2 ,2
1
(96% e e l
>
Lindell, S.D.; Elliott, J.D.: Johnson, W.S. Tetrahedron L e t t , (19841,
R = "CgH19
85b
'*
26,
6197
;02Ph
HOH
Eisch, J.J.*: Dua, S.K.; Behrooz, M. -J Org Chem, ( 1 9851,
84%
2,3674
32
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . 2Ca, EDA
0
CH3(CH213CH-CH2
Benkeser, R.A.
2 . a q . NH4C1
* ; Rappa,
A.;
91 x
Wolsieffer, L.A. them, (19861,
-J Org
1 . 2.2Ca, NH3 2h
* ; Chua,
Khoudary, K.P.:
V.: Schroeder, J . E . ; Barrans Jr., R.E.: Wang, N.: Wetzel, J . M . -J Org Chem, (1 986) , 51, 4731 CH2=CHCH2SiMe3
Oku,
51, 3391
*
2 . a q . NH4V1
Hwu, J . R .
OH I CH3(CH2)3CHCH3
*
/ \
SECTION 39
*. A . , Homoto, / \
CH2=CH-CH-CH2
TiCl 4 , CH2C1 - 8 5 " C , 5h'
Y.; Harada, T.
Ph
I
+ CH2=CHCH2C (CH2) 30H
I
Ph
quant. Chem Lett, (1986), 1495 --
M e L i / S m [ N ( T M S ) 2]3 E t 2 0 , RT, 2 3 h
Mukerji, I.; Wayda, A.
* : Dabbagh,
> CH2=CHCHCH20H 81 %
*
G.: Bertz, S.H. A r q p --Chem Int Ed (19861, 25, 760
m,
SECTION 40
33
ALCOHOLS FROM H A L I D E S
Reviews : "Cleavage of Ethers" Bhatt, M.V.;
K u l k a r n i , S.U.
Synthesis, (1983), 249
"Synthetically Useful Reactions of Epoxides'l Smith, J.C.*
Synthesis, (1983), 629
SECTION 40: Alcohols --and Thiols from Halides and Sulfonates 1 . MeSBCH2-
-n C 6 H 1 3 B r
*
2. o x .
"CgH13
CH 2OH
92%
Pelter, A . : Williams, L.: Wilson, J.W.: Singaram, B. Tetrahedron Lett, (1983), 3, 627, 631
I.\
1 . ( iPrO)2MeSiCH2MgC1
,'
Tamao, K .
10% c u r
* ; Ishida,
N.:
Kumada, M.
*
J Org Chem, (1983), 48, ---
91 % 2120
1 . M g , THF m
B
Me0
r
2 * [ o0' 'B-o-o-tBu THF,
overnite
3 . 2P: H C 1 ,
0°C
*M e 0 91 %
Hoffrnann, R.W.:
Ditrich, L.
Synthesis, (19831, 107
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
34
1. nBuLi, THF,
2. 0::B-H
SECTION 40
-100°C
, THF
3 . 30% H 2 0 2 ,
1 0 % NaOH, 2 5 ° C 32%
* Danheiser, R.L. ; Savoca, A.C. Br
J Org Chem, (19851,
50, 2401
80°C
Pd[PPh3I4.
t nBu3SnCH20H,
dioxane
20h
52%
*
Sumiya, T.; Ohhashi, K.: Sano, H.: Migita, T. Chem Lett, (19851, 997 --
Kosugi, M.:
1 . [(Et3P)2Ni/NaHCNBH3]
I
( N H 2 ) 2 C = S , DMF, 6 0 ° C
2 . a q . OH3. aq. HC1
Takagi , K .
*
s
*
Chem Lett, --
t
93
x
( 1 9851, 1307
-n C 3 H 7 C H 2 C1
benzene
*
20"C, 28h
nC3H,CH2SH 65%
Molina, P. ; Alajarin, M.; Vilaplana, M.J.; Katritzky, A.R. Tetrahedron E,( 1 9851, 26, 469
t
SECTION 42A
A L C O H O L S FROM K E T O N E S
1 . H2S,
.
'TMS-C1,
2. nBuLi
Harpp, D.N.
PhCH2Br
* : Kobayashi, M.
Py
*
CH3CH,CH2CH0 3.
35
PhCH2SH
50%
Tetrahedron Lett, (19861,
3,3975
9 II
1 . NaOCH, I B u 4 N B r
n C 8 H 1 ,-C1
125"C, 1 . 5 h 2. aq.
NaOH,
Zahalka, H.A.: Sasson, Y.
*
>
nC8Hl
RT
,-OH 91%
Synthesis, (19861, 763
SECTION 41: Alcohols --and Thiols from Hydrides
No Additional Examples SECTION 42: Alcohols --and Thiols from Ketones
The following reactions types are included in this section:
A. Reductions of Ketones to Alcohols. B. Alkylations of Ketones, forming Alcohols. Coupling of ketones to give diols is found in Section 323 (Alcohol - Alcohol). SECTION 42A: Reductions
of Ketones to Alcohols
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
36
0
Asymnetric Reduction:
!I
*
RCR'
SECTION 42A
0
1 *
RCHR'
OH R = Pr = Ph
R'
H
NH2
Ph
*
Itsuno, S. ; Ito, K.; Hirao, A.:
''
Nakahama, S.
JCS Chem C a m , (19831, 469 -J Org C h m T 1 9 8 4 ) , 9, 555
Q-
R = Me R'= Ph
(96% ee R )
30°C
, HSiHPh2
11
N
99%
*
A"'/H 2 . HOH ( 8 3 . 2 % ee R ) Ph Me Brunner, H. ; R i e p e l , G : W e i t z e r , H . &ew Chem I n t Ed Engl, (19831, 22, 331
*
R
R'
=
Me
= Bn
*
1 . HSiHPh3/[Rh(COD)C1I2 t 2 . H30
Brunner, H. ; Becker, R.: Riepel, G. Organanetallics, ( 1984 1, R
= P r
R' = Ph
S,S'
( 5 2 . 7 % ee R )
3,
I@I fOOH [PhCNH-CH-CH2-S12
LiBH4,
-
tBuOH/THF
Soai, K.*; Oyamada, H.: Yamanoi, T. R = Bu
91 %
t
1 354 98%
t
(90% ee)
JCS Chem Ccutn, (1984), 413
THF quant. ipr
JCS Perkin I, (19831, 1673 ---
SECTION 42A
PhCH3,
-78OC,
BF3
= Ph
71 %
*
R = iPr R'
37
ALCOHOLS FROM KETONES
(67% e e R )
Ph
Allwood, B.L.; Shahriari-Zavareh, H.; Stoddart, J.F.: Williams, D.J. JCS Chem Coam, (19841, 1461
---
R = Me R'
iPrOH.
NADP,
61 %
TRI-HC1 ___)
= i P r
Keinan, E.
37OC.
(86% e e )
T B A D H , HSCH2CH20H, pH 8 . 5
* ; Hafeli,
R = Ph R ' = Me
E.K.; Seth, K.K.: Lamed, R. J Am Chem Soc, (19861, 108,162 ----
iPrOH,
Ir(COD)(acac),
(rnenthyl )Ph2P,
HBF4,
Krause, H.W.; Bhatnagar, A.K. J Organmt 0
R = Ph R' = E t
1.
Ph?NH$'
2. aq.
*
-
83°C
-,
IB( 0 OtBu
KOH
(1 9861,
,
Soai, K. ; Yamanoi, T.: Oyamada, H.
( 4 2 % ee R )
302,
265 71 %
L i , THF
3 . a q . NaHC03
tic1
87%
*
t
(88% ee)
Chem Lett, (19841, 251
R = Ph
-1 R'
- ;E: (A>:$(
= Me
60% O O O C
(95% eel
\
*
Noyori, R. ; Tomino, I.; Tanimoto, Y.: Nishizawa, M. 106, 6709 J Am Chem Soc, (19841, ---R = Ph R ' = Me
v
Cervinka, 0 .
1 . LiAlHll3
-------_.I_
2.
(-)-quinine,
a q . H2S04
20 _-___-___E t -m
quant.
(98% e e )
Fsbryovi, A. ; Sablukova, I. Coll Czech Chem Comn, (19861, ----
51, 401
38
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
R = Et R ' = Ph
SECTION 42A quant,
NH2
THF
*(70%
ee R )
*
Itsuno, S. ; Nakano, M.; Ito, K.: Hirao, A.: Owa, M.; Konda, N . ; Nakahama, S. JCS Perkin I, (1985), 2615 --NaBH4,
(*)-tartaric
acid
TH F
Adams, C.*
Syn Cornnun, (1984), 1.
W OH OH
14,955
LiA1H4/AlBr3/Et20/-20°C
3.
2N HC1
4.
Cl,CbCl,
5 . NEt3
CH2C12/DMS0
(91% eq)
+ RT
80%
Mori, A.: Fujiwara, J . ; Maruoka, K.; Yamamoto, H. * Tetrahedron E,(19831, 24, 4581 -78°C
(95% ee)
1. Dibal-H
X ' P*', h
MsO
CH2C12. 2.
,
, Py-H+Tsbenzene
2.
00
qua n t
Et3A1
-78°C 83%
(95% eel
*
Suzuki, K.; Katayama, E.; Matsumoto, T.; Tsuchihashi, G. Tetrahedron Lett, (1984), 25, 3715
39
ALCOHOLS FROM KETONES
SECTION 42A
Non-Asmetric Reduction: t B u M g C 1 , Et,O, -
'
Me
Maruoka, K.; Sakurai, M . ; 1 . FAD,
= MAD
* Yamamoto, H. Tetrahedron Lett,
PhCH3
-
b
2. MeLi Maruoka, K . ; I t o h , T . ;
HO
-23°C
(ax:eq = 1:9) ( 1 9851,
(ax:eq
*
Yamamoto, H. J Am Chem Soc, (19851, ----
26,
3853 8 4Z
= 1 :99)
107,4573
93%
B3H8 = o c t a h y d r o t r i b o r a t e Tamblyn, W.H. Dao, T.V.
* ; Aquadro,
R.E.;
DeLuca, O . D . ;
Weingold, D.H.;
Tetrahedron Lett, (19831, iPrOH,
2,4955
autoclave
Cp2ZrH2,
30°C 92%
*
I s h i i , Y.*; Nakano, Ogawa, M.
T.: Inada, A , ; Kiohigami, Y.; S a k u r a i , K.;
-J Org Chem,
( 1 9861,
51,
240
40
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0
PPNtHCr(C0)3-,
II
CH3CH2CCH3
PPN
AcOH,
THF
25°C
*
SECTION 42A
OH
1
CH3CH2CHCH3 70%
= fi(tripheny1phosphine)irnminiurn
Gaus, P.L.*; Kao, S.C .*; Youngdahl, K. : Darensburg, M.Y. J Am Chem Soc, (19851, 107, 2428 ---0 it
C H 3 (CH2) 2CCH3
ZrOCl 2.8H20/H20 iPrOH , ref1 ux
* Matsushita, H. ; Ishiguro, S.; Mizusaki, S.
*
OH
I
*CH~(CH~)~CHCH~ quant
Ichinose, H.; Izumi, A.:
-Chem Lett,
(1985), 731
*Jy
1 . P h 2 S b H , THF, A 1 C 1 3
RT
2. a q . H2S04 Huang, Y.Z.:
Shen, Y.C.; Chen, C. Tetrahedron E, (19851, nBu3SnH, MeOH,
96%
26,
5171
55OC
1400 m P a , 24h
* A. ; D a h a n ,
Dequeil-Castaing, M.: Rahm, N. -J Org Chem, (19861,
quant
51,
1672
+'" 41
ALCOHOLS F R O M KETONES
SECTION 42B
1 . HSCH2CH2SH, H t 32 . H3 O cH B u L i / E t 2 0
89%
*
61,74
Org Syn, (1983),
Wilson, S.R. ; Georgiodis, G.M.
SECTION 42B: Alkylation of Ketones, Forming Alcohols
Aldol reactions are listed in Section 330 (Ketone-Alcohol). 1 . PhCH2SiMe3, T H F nBu4NF, O°C
PhCCH3
OH
I
t
2 . H30t
PhCCH2Ph
I
CH3
Tetrahedron Lett, (19831,
Bennetau, B.; Dunogues, J.
2 MI2, THF,
R
R
=
LBu
* Molander, G.A. : Etter, J.B.
3, 4217
RT
Yb
95%
(Z:E
=
M = Sm
95%
(Z:E
= 1 .1 . 5 )
M
R = H
75%
=
1:l .3)
J Org Chem, (19861, 51, 1778 TetrahGfi (1984), 25, 3281
0
II
PHCH2CCH3
*
m,
MeTiCl 3 , E t 2 0
- -
- -
O'C,
_.I-_
2h
Reetz, M.T. ; Kyung, S.H.; Hullmann, M.
OH
>
I
PhCH,CCH 3
Tetrahedron, ( 1 986), 42, 2931
C H 3 81%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
42
1 .nBuCeC12, -78°C
2.
aq.
SECTION 42B
THF
NH4C1
88%
* Imamoto, T. ; Sugiura, Y.;
Takujama, N. Tetrahedron E ,( 1 9841,
25, 4233
78%
Cooke Jr., M.P.*: Houpis, I.N. Tetrahedron Lett, ( 1 9851, 1 . 57% H I
0
iI
PhCCH=CH2
*
2.
Zn,
TMS-C1, heat
THF
26, 4987
Ph,OH
n
e
68%
Narasimhan, N.S. ; Patil, P.A. Tetrahedron E,( 1 986), 27, 51 33 Reviews:
l'Metal-Ammonia Reduction of Cyclic Aliphatic Ketones1' H u f ' f m a n , J.W.
*
Accts Chem Res, ---
(1983), 16, 399
"An Introduction of Chiral Centers into Acyclic Systems Based On Stereoselective Ketone Reductionf1 Oishi, T., Nakata, T.
--Accts Chem Res,
(19841,
17,338
lfMicrobialAsymmetric Catalysis - Enantioselective Reduction of Ketones" Sih, C.J.
* : Chen, C.-S.
Angew Chem Int Ed Engl, ----
( 1 984),
23,
570
A L C O H O L S FROM OLEFINS
SECTION 44
"Stereoselective Acyclic Ketone Reduction"
43.
*
*
Nakata, T. ; F u k u i , M.; Ohtsuka, H.; O i s h i , T. Tetrahedron, (19841, 3, 2225 TtMechanismand Stereochemistry of Alkali Metal Reductions of Cyclic and Unsaturated Ketones i n Protic Solvents" Pradhan, S.K.
3c
Tetrahedron, (1986),
42,
6351
Related Methods: Alcohols from Aldehydes (Section 34) SECTION 43: Alcohols and Thiols from Nitriles
-
No Additional Examples SECTION 44: Alcohols --and Thiols from Olefins For the preparation of diols from olefins see Section 323
(Alcohol - Alcohol).
6
Taylor,
* R.T. ; Flood,
(E:Z
L.A.
Co(TPP),
DME/iPrOH
HoY * f i
TPP = meso-tetraphenylporphyrinato
*
1:l)
J Org Chem, (1983), 48, 5160
Et4BBH4, 02, 2 d
Okamoto, T. ; Oka, S.
=
'9 I
J Org Chem, (1984), 3,1589
87%
44
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
NaBH4, T i C 1 3 ,
THF
*
..
PhC=CH2
18-crown-6,
30°C
Lee, H.S.:
* Isagawa, K. ; Toyoda, H.;
SECTION 44
PhCHCH20H
l h
Chem Lett, --
84%
Otsuji, Y.
( 1 984), 673
1 . L i C H C 1 2 , THF
-
-1CO"C
* CH3(CH
25°C
2 . NaOMe/MeOH
/OH ) CH 5 \
3 . NaOH/H202
Brown,
* H.C. ; Imai, Y.; Perumal, P.T.; Singaram, B. -J Org Chem, ( 1 985), 50, 4032 1.
B
&l,Li.0Et2. MeI,
2 . HOCH2CH20H, THF, t
Masamune, S. ; Kim, B.M.: S.J.
9.5h E t 2 0 , RT
6N NaOH/MeOH
30% H202,
50°C
Soc,
-*'d 89%
(97% ee)
Petersen, J.S.:
---J Am Chem
63%
Sato, T.: Veenstra, (19851,
107, 4549
1 . HSiMeEt2 RhCl ( P P h 3 ) 3 Me02C-(CH2)8CH=CH2 2 . Me3N-C,
KHF2,
Sakurai, H.
* : Ando,
w MeC2C-(CH2)10-OH
DMF
130°C
72%
*
M.: Kawada, N.; Sato, K.: HosOmi, A . Tetrahedron E ,( 1 986), 3, 75
SECTION 45
Review:
45
ALCOHOLS FROM M I S C .
"The Use of Chiral Organoboranes i n Organic Synthesis"
Matteso, D.S.
*
Synthesis, (19861, 973
SECTION 45: Alcohols and Thiols from Miscellaneous Compounds
Fleming,
* I. : Henning,
R.
: Plaut,
7 4%
H.
1 . Me3SiCH2CH=CH2, 2. 3.
TiC14,
JCS Chem C m , ( 1 984), 29 CH2C12
S
-75°C b
HOH
4. 2 . 2 L D A , T H F (94% ee R)
Seebach, D.
* : I m i n k e l r i e d , R.: Stucky, G. Angew Chem Int Ed Eslgl, ---1 . NaBH4, THF-MeOH r e f 1ux
PhSSPh 2. aq.
HC1
* K.
Ookawa, A.: Yokoyama, S . : Soai, =Cornnun,
(1986),
-
( 1 986),
16,819
For conversions of boranes t o alcohols (Section 4 4 )
7 6%
25, 178
PhSH quant,
46
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 45A
SECTION 45A: Protection of Alcohols and Thiols 1. 2
S.
(-gB-" , CH2C12,
-78°C 45 m i n
2 . a q . NH4C1
MEMO
9
Williams, D.R.
* ; Sakdarat,
HO 91 %
S.
Tetrahedron E,( 1 983),
3 Me2BBr, -78"C,
OMEM
2,3965
CH2C12
l h
OH 9 5 %
(MOM)
* Y. ; Yoakim,
Guindon,
(94%)
C . ; Morton, H.E.
-J Org Chem, Tetrahzn
OMOM
d
Me3SiBr,
(19841, 49, 3912
E,(1v83), 24,
3969
CH2C12
4a s i e v e . - 3 0 ° C 97%
Hanessian, S.*: Delorme, D. Duf'resne, Y. Tetrahedron Lett, (19841,
25,
2515
1 . Me3SiC1, N a I , CH3CN -2OoC,
30 min
",,,
2 . Me3SiC1, N a I -2OoC, 30 m i n Tetrahedron Lett, (1984), Wilson, J . Z .
"'OMEM
Rigby, J.H.*:
-
93%
3, 1429
SECTION 45A
47
PROTECTION O F ALCOHOLS
-
1 . e , AcOH, NaOAc P t electrodes 2.
K2C03,
a q . MeOH
77% Mandai, ,T.; Yasunaga, H.: Kawada, M.; Otera, J . Chem L e t t , (19841, 715 -OMTM
Chowdhury, P.K.;
*
*:
Sharma, R.P. Batuah, J.N. Tetrahedron E,(19831, MeOCH20Me ( s o l v e n t .-
0
H
Olah, C1.A.I:
24, 4485
1 S " O M
95%
l h
Husain, A.:
Narang, S.C.
,C8 n
,
CH2=CH 'CH3 --..-
Synthesis, (19831, 896
c a t . PdC12(COD)
~
96%
Ph C H 2 ) 3 0 H
-
t CH J P h ( C H 2 ) 3 0 CIO B n
I H,,
Mukaiyama, T.
8 0%
.
TMS- I 6
OH
*
5 % Pd-C
Murakami, M. Chem L e t t , ( 1 9841, 265
Ohshima, M.:
--
CH3
48
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . 5 (iPrS)2BBr, -95°C
QMEM
?
CH2C12, 5 m i n 2. M e 2 N o
t-Bu
3. a q . K 2 C 0 3
* E . J . ; Hua,
Corey,
, -95"~
S e i t z , S.P.
D.H.:
Y.: Shibasaki, CH =C
Tetrahedron Lett, (19841,
* M.
,OBn
92%
25, 3
0
*
FH 3 I
Ph(CH2)30COBn I
F H+ resistant
quant. M.: Nagaoka, H . ; Murakami, M . Chem Lett, (1984), 615 -BrSiPhtBu(OMe), NEt3
*
Ohshima,
quant. OH
25, 663
, PdC12(COD)
f--
T.
96%
Tetrahedron Lett, (1984),
'CH~F -C H 3 C N , RT quant. H2, 5% P d - C
Ph(CH2)30H
Guindon, Y.
t-BU
2 . a q . KHC03 0s i M e 2 t B u
OTH P
Mukaiyama,
GCH2S(
-0
1 . 2 Me2A1C1, CH2C12
Ogawa,
SECTION 45A
Ph I
nBu4NF, DCE 90% Fortin, R.;
OSi- t - B u
&Me
Yoakim, C . ; G i l l a r d , J.W. Tetrahedron Lett, ( 1 9841, 25, 471 7
SECTION 45A
49
P R O T E C T I O N OF A L C O H O L S
n
0
w0
b *
HC1
CuBr2/THF -.
,
85%
EtOH/HOH
--- - - -
. .
r e f 1ux
90%
>
-
20h
RT,
*
,
-
-
__
Fetizon, M. ; Hanna, I.
Synthesis, (19851, 806
THPO(CH2)40H
RT
DEAD, CAN,
99%
aq.
THPO(CH2)40As
CH3CN As =
4
0 . O M e
Fukuyama, T.*: Laird, A . A . : Hotchkiss, L.M. Tetrahedron Lett, ( 1 9851, 1 . Me2BBr, 2.
CH3SH,
CH2C12,
6,' os&-
\
f
Collington, E.W.;
-78°C
,
-78°C
J Org Chm, (1985),
3,5379
91 %
I. a q . HF, C H ~ C N 2.
OSi
6291
iPr2NEt
CH2C1
* Morton, H.E. ; Guindon, Y.
26,
aq.
NaHC03
1. nBu4NF/THF, 2.
aq.
)f;ioQJoH /
-
96%
0°C
NH4C1
* Flinch, H. ; Smith, I.J.
Tetrahedron E ,( 1 9851,
96%
26, 681
50
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 45A
quant. Boeckman J r . , R.K.*; King, P.F.
HO
Potenza, J . C .
* ; Stroud,
t-Bu
26, 1411 Tetrahedron Lett, (1985), 26, 1415
Tetrahedron=,
S.C.
(1985),
\
tBuMe2SiOTf 18-crown-6, CH2C1 RT,
Braish,
T.F.: Fuchs, P.L.*
Related Methods:
l h
54%
Syn Cornnun, (1986),
16, 111
Esters from Alcohols (Section 123) Alcohols from Ethers (Section 39) Esters from Alcohols (Section 108) Alcohols from Esters (Section 38)
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 4 PREPARATION OF ALDEHYDES
SECTION 46: Aldehydes
Acetylenes
No Additional Examples SECTION
--+Derivatives
3: Adehydes from Acid
(LCOOH
L
1 . C1HC=NMe2 C 1 - , -30°C 2. LiA1H(OtBu)3,
A
Py
CuI
&CHO
*
A
3 . H30+
* Fujisawa, T. ; Mori, T.;
A
Tsuge, S.: Sato, T. Tetrahedron E,(1983),
THF,
0°C
-
*
Eyman, D.P.; W i e m e r , D.F. J Org Chem, (1984) , w B H C 1 .SMe2,
8 3 5'
s, 2279
CH2C1
Ph2CHC02H
Ph2CHCH0 O°C
Brown, H.C.
1543
reflux
6h
H u b e r t , T.D.;
24,
8 0%
* ; Cha, J.S.;
-
RT,
1 5 min
Nazer, B.; Yoon, N.M. (19841,
-J _ Am-Chem - Soc,
91 %
106,8001
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
52
OH
NaC10,
1
PhbHCOOH
2h
Carlsen, P.H.J.
PhCHO 95%
RT
Acta Scand B, ---
0
II
+
@NMe3
C H 3 ( C H 2 ) 1 gCC1
@
t
E t20/HOH
*
SECTION 48
BH4
(1984), 343
-
0
*
!I
C H 3 ( C H 2 ) 1g C H
hexane = Amberlyst A-26
93%
GOrdeev, K.Yu.; Serebrennikova, G.A.;
J Org Chem ----
Evstigneeva, R.P. USSR, ( 1 9851, 2393
21,
SECTION 48: Adehydes Prom Alcohols -and Thiols PhSePh,
PhCH20H
PhCH3,
Takai,
* K. ; Yasumura,
NCS
t
PhCHO
DBU 93%
M.;
Negoro, K.
-J Org
Chem, (1983),
48,
54
COOH
RuCl 2 ( P P h 3 ) *
Muller, P.;
Godoy, J.
Helv Chim Acta, ---
quant.
(19831, 66, 1790
SECTION 48
53
ALDEHYOES FROM ALCOHOLS
TMP,
0.3
TEMPO,
2h,
RT
L i C l O4
CH3CN
*
Semmelhack, M.F. ; Chou, C.S.; Cortes, D.A. J Am Chem Soc, ( 1 9831, _---
CH2=C
,CH 3
P ~ ( O A C ) ~ P, h I
\
NEt3,
CH20H
100°C,
Buntin, S.A. : Heck, R.F. (OH
*
105,4492
y3 t
CH3CN
5 9%
PhCH2CHCH0
l l h
82%
Org Syn, (19831,
61,82 CHO
Ce(OH)302H Ph-H,
reflux 95%
Firouzabadi, H.; Iranpoor, N.
Cornnun, (19841,
111, 875
95%
Firouzabadi, H . ; Iranpoor, N . ; Hajipoor, G.; Toofan, J.
-Syn Cornnun,
(1984),
fi, 1033
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
54
SECTION 48
95%
*
Firouzabadi, H. ; Sardarian, A.R.; Naderi, M.; Vessal, B.
40,
Tetrahedron, ( 1 9841,
NaC103,
Os04
E t 2 0 , g l . AcOH
*
H OH
HO
Maione, A.M.; Romeo, A.
*
HO
30%
Synthesis, (19841, 955
P d ( O A c ) 2 , NaHC03 CH3CH2CH2CH20H
0'"
5001
nBu4NC1,
PhI
*
CH3CH2CH2CH0
DMF, RT, 48h 80% Kantam, M.L.; Jamil, Z.
* Choudary, B.M. ; Reddy, N.P.;
-
Tetrahedron Lett, (19851,
26,
6257
COOH ( @)2cr207
PhCH=CHCH20H
H
(2.5 eq) t PhCH=CHCHO
30 m i n
Lopez, C.; Gonzalez, A.: Cossio, F.P.:
* Palomo, C.
B c o m n U n , (1985),
80%
15, 1197
SECTION 48
ALDEHYDES FROM ALCOHOLS
/OH
55
CHO
LAPA- E DA 130"C,
17h 7 4% (95% Z)
LAPA = l i t h i u m 3 - a m i n o p r o p a n a m i d e
* H.M.R. ; Ktiver,
6
Hoffmann,
1 . Ph2SbBr,
\I
Br
2. Br2,
*
Huang, Y. ; Shen, Y.
-6
Pauluth, D.
A.;
JCS Chem Comn, (1985), 81? --Et2NH,
RT, 2 h 1O"C,
PhH
lOmin
Br
Synthesis, (19851,
; Chen, C .
62%
651
CHO
4h
Sur, M.; Adak, M.M.;
Pathak,
* T. ; Hazra,
63% B.; Banerjee, A .
Synthesis, ( 1 9851,
652
PVPCC
Il-CH2PPh)3RhC1, x y l ene,
H2
100°C
PVPCC = p o l y ( v i n y l p y r i d i n i um)c h l o r o c h r o m a t e
. .* ; Chandran,
Bergbrei ter , D E
R.
---J Am Chem Soc,
(1985),
107,
80%
4792
56
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 49
,OH
CHO
I
*
Yamamoto, J. ; Ito, S . : Tsuboi, Ta.; Tsuboi, Ts.; Tsukihara, K. B u l l Chem Soc Jpn, (19851, 2, 470 ---H3C\ Ph
/"
/CH2@H =c\
( P h 3 P+ ) 2 C H 2 C r 2 0 7 - 2
H
CH2C12, 25"C, 12h
/CHO
Ph
H
/c =f
t
* Cristau, H.-J. ; Torreilles, E.*; Morand, P.:
H3C\
Christol, H.
75%
Tetrahedron Lett, (19861,3, 1775
CH~(CH~)~CH~OH PhH, K2C03 r e f l u x , 90 m i n
*
*
CH3(CH2)5CH0 68%
Mihailovic, M.L. ; Kostantinovic, S.; Vukicevic, R. Tetrahedron Lett, ( 1 986), 3, 2287 Review: TTChromim(VI) Based OxidantsT1
*
Firouzabadi, H. ; Iranpoor, N.; Kiaeezadeh, F.: Toofan, J. Tetrahedron, (1986), g, 719 Related Methods: Ketones from Alcohols and Phenols (Section 168) SECTION 49: Aldehydes from Aldehydes
Conjugate reductions and Michael alkylations of conjugated aldehydes are listed in Section 74 (Alkyls from Olefins).
SECTION 51
ALDEHYDES F R O M A L K Y L S
57
1 . TMS-C1
0
2 . CH212/Zn-Cu
n~ H C H 2 C H O - 4 9
:-.
Giese, B.*:
3 . Hg(oAc)2/AcOH
4. CH2=CHCN, NaBH4 5 . KF Horler, H. Tetrahedron=,
II
*
HCCH(CH~)~C=N
I
60%
(1983), 2,3221
e-, P t electrodes
MeOH, NaOTs
*
28 "C
b r a , J.; Smigielski, K.; Kula, J.
r:M
llC4Hg
60%
Synthesis, (1986), 586
Review: 'IAlkylation of Ketones and Aldehydes via Nitrogen
Derivatives"
Synthesis, (19831, 517
Whitesell, J.K.; Whitesell, M.A.
Related Methods: Aldehydes from Ketones (Section 57) Ketones from Ketones (Section 177) Also via: Olefinic aldehydes (Section 341)
6
SECTION 50: Aldehydes f m Alkyl, Methylenes, and Aryls
OMe
1 . e-, C electrodes Et4NOTs, MeOH/AcOH
2 . a q . H 2 S 0 4 , 3 h , RT t
Nishiguchi, I. ; Hirashima, T.
J Org Chem, (1985),
SECTION 51: Aldehydes from Amides
No Additional Examples
OMe
50, 539
78%
58
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 53
SECTION 52: Aldehydes from Amines
PhCH2NH2
1 . mTFMB, 6KOH, E t O A c -78"C, 7h
t
PhCHO
2 . 1 5 0 " C , 2 . 5 N HC1 TFMB = ( t r i f l u o r o m e t h y l ) b e n z e n e s u l f o n y l p e r o x i d e
Hoffman, R.V.*;
Kumar, A.
J Org Chem, (1984),
-
77%
3,4011
Related Methods: Ketones from Amines (Section 172) SECTION 53: Aldehydes -from Esters
1 . 2NaH/THF MeSCH2S02Tol 2 . NaBH,, MeOH -r 3. K2C03
c
* Ogura, K. ; Yahata, N.;
~
M e O .- O C H O
91 %
Takahashi, K.; Iida, H. Tetrahedron E ,(1983), 24, 5761
1 . LTMP, C H 2 B r 2 , - 9 0 ° C TH F 2 . C B u L i , -90°C 3.
Q
4.TMS-C1
,
* Kowalski, C.J. ; Haque, M.S.
0-
0
OCCH3
"
-90
ruflux
- 0°C 5.H' J Am Chem Soc, ----
3 HSiEt2Me 50 a t m C O
4% c 0 2 ( c 0 ) 8
1
68%
(19861, 108,1325
0 " 0-
0s i MeE t 2 7 5%
Chatani, N.; Fujii, S.; Yamasaki, Y.; Murai, S.*; Sonoda, N. J Am Chem Soc, (19861, 108,7361 ----
SECTION 55
SECTION
ALDEHYDES F R O M H A L I D E S
2:Aldehydes from Ethers,
Epoxides,
*
Thioethers 0
I1 ur
1. nBuLi
Maddaluno, J.; d'hgelo, J.
59
Tetrahedron E ,( 1 9831,
2, 895
Related Methods: Ketones from Ethers and Epoxides (Section 174) SECTION 55: Aldehydes from Halides and Sulfonates 1 . PhSCH2SiMe3, n B u L i TME D A
CH3CH2CH2Br
6
Ager, D.J.
CH3CH2CH2CH0
2 . HOH
JCS Perkin I, ---
(1983), 1131
atm CO
4% Pd[PPh3I4,3 PhCH3,
50°C
-6
*
Baillargeon, V.P.: Stille, J.K. ---J Am Chem Soc, (19831, Br
1 . Mg, THF 2 . H C 0 2 L i , THF, 3. cat.
70%
65%
105,7175 CHO
reflux
e- b e n z o q u i n o n e
E t 2 0 , d i l , HC1, 0°C
85%
' * Bogavac, M.; Arsenijevid, L.'; Pavlov, S.; Arsenijevic, V. Tetrahedron E ,(19841, 3 , 1843
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
60
SECTION 55
CHO
I Wph314
, 3
co
atm.
n B u 3 S n H , THF, 50°C Br
Br
*
Baillargeon, V.P.: Stille, J.K. J Am Chem SOC, (1986), ----
70%
108,452
P t C l 2( PPh3)2 , 120°C
dioxane,
9h 86%
*
Takeuchi, R.; Tsuji, Y.; Watanabe, Y. JCS Chem C a m , (1986), 351 --1. Li,
DMF,
1 8 " C q 9))))
PhBr
2 . H30
t
*
PhCHO 81 %
*
Einhorn, J.; Luche, J.L. Tetrahedron Lett, ( 1 986), 3, 1791, 1793
dioxane, 3h
r e f 1 ux
85%
*
Ferraboschi, P.; Azadoni, M.N.; Santaniello, E. ; Trave, S. Comnun, (19861, 16,43
ALDEHYDES FROM KETONES
SECTION 57
DMSO. NaHC03
CH3(CH2)6CH2Br
115°C. N a I 2h
Dave, P. ; Byun, H.-S. ; Engel,
* R.
61
CH3(CH2)6CH0
>
-Syn Cornnun,
60%
16,1343
(1986),
SECTION 56: Aldehydes from Hydrides
HO
@ \
t
\
Smith, R . A . J .
HC)
(PhS)3CH, CH2C12 M e 2 S - S M e BF4RT. 2 h
* ; Bin
Manas, A.R.
7 0%
CHO
Synthesis, (19841, 166
SECTION 57: Aldehydes from Ketones
39% E , 3 7 % 2 Tortajada, J.; van Hemelryck, B . ; Morizur, J.-P.
4s 0
Moskal, J . ; van
CH20H
x
Tetrahedron, (1984), 40, 613
,N E C
1 . LiCH,
P(OEt )
II
0
2.
a q . HC1
, THF
- --
->
CHO
* 97% Leusen, A.M. Rec Trav Chim Pays Bas, (1986), 105,141 ---
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
62
SECTION 59
SETION 58: Aldehydes from Nitriles
No Additional Examples SECTION 59: Aldehydes from Olef'ins 2H,/CO
O H C ( C H ~ 5)
~
L'
CH~=CH(CH~),CH=CHCH,
P h H , RT
c a t = Rh(H)Co(PPh3I3
cat.
CHO
~
47%
CH,CH(CH~),CH=CHCH,
JCS Perkin I, ---
(1)
(1983), 1929
1 . BHBr2.SMe2/pentane 2 . HOCH2CH2CH20H
Q -
3. s e c B u L i /MeOCH 2 S P h / T H F 4. HgC12
Brown,
(12)
+
=
1
Grigg, R. * ; Reimer, G.J.; Wade, A.R. I
~
* H.C. ;
Imai, T.
5. H202,
2 Am
Chem
"""CHO
pH 8 SoC,
(1983),
1. e P t electrodes N a B r , CH3CN/H20 2. 1 % a q . H2SOb 3 . e - , P t e l e c t r o d e s , 65°C aq. NaOH/PhH
Torii, S.; Uneyama, K.; Ueda, K.
* Kikuchi, H. ; Kogure, K.;
105,6285
53%
CHO
97%
J Org Chem, (19841, 49, 1830
3h
Toyoda, M.
Chem Lett, --
92%
(1984), 341
~
~
SECTION 60
63
ALDEHYDES FROM M I S C .
Related Methods: Ketones from Olefins (Section 179) SECTION 60: Aldehydes Miscellaneous Compounds
v2
1. Dibal-H,
'
24h
>
32 . A NC 1 2S 0 3
/'
0L - 0
4.
Si02
L
*
Meyers, A.I. ; Himmelsbach, R.J.; Reuman, M. J Org Chem, ( 1 9831, Me0
\
pcH O 62%
48,
4053
1. LBuLi
/OMe
B rI C '"\H
2. 2Bu3B 3.
BF3*0Et2
nBuCH2CH0
+
4 . a q . HC1
Koshino, J.;
* Sugawara, T.; Yogo, T.;Suzuki, A . Syn Camnun, (1983), 13, 1149 1 . KOH,
CH3(CH ) C H N O
MeOH
>
2 . c o n c . a q . KMn04 M g S 0 4 , MeOH,
* Steliou, K. ; Poupart, M.A. Ph
CH3(CH2I6CHO 83%
0°C
J Org Chem, (19851, 50, 4971
HOCH2CH20H,
CI
6h
80°C
>
ph
[t PhCHO,
Liu, M.T.H.; Kokosi, J.
82%
Heterocycles, ( 1 9851,
65% 30%]
23, 3049
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
64
1. CBuLi, 2.
-20°C C H ~ ( C H ~ ) ~ C H O
CH2C12
90%
-20°C * Julia, M. ; Rolando, C.
Tetrahedron E ,( 1 9851,
ICgH13
1 . A1Me3,
DCE
25"C,
12h
0 >.kNMe2 0
0
-78°C
hexane/THF
3 . mcpba,
'$
,
(b!e0)2BC1
CH3(CH2)5CH2S02Ph
Baudin, J.-B.;
THF,
2 . 03/MeOH,
CNMe2
Maruoka, K.; Nakai,
S.:
26, 2333 y 3
jnC6H1
-78°C
, II
%
SECTION 60A
85%
(S:R
( 9 5 % ee,S
Sakurai, M.; Yammoto, H. Synthesis, ( 1 986 1 , 1 30
3CHCH0 = 6.4:l)
3
SECTION 60A: Protection of Aldehydes 1.
CH 0
@-CH(OH)CH20H/PhH
CHO
pTsOH , h e a t
I
1
2 . B2H6
(CH2)8
I
3 . Me3N+0
CH =CH
*
0
4 . PY, PhlCl 5. a q . d i o x a n e , pTsOH
*
Hodge, P. ; Waterhouse, J.
(CH2)g 1 CH 2 0 C P h
--JCS Perkin I,
(19831, 2319
S i (OMe)4
CH3CH2CH0 -78OC
*
-
11
0
65%
,OHe
t 0°C
'
CH3CH2CH2CH
91 %
Sakurai, H. ; Sassaki, K.; Hayashi, J.; Hosomi, A. , (19841, 2, 2808
OMe
SECTION 60A
65
PROTECTION OF ALDEHYDES
N02 G C H 2 0 H
CH3(CH2)7CH0
,
8-naphthol eS03H
*
(Fle0l2CMe2 85%
<
* . 'O
CH3(CH2)7
0
7
Gravel,
PhH,
* D. ; Murray,
hv
95%
S.: Ladouceur, G. JCS Chem Comn, (1985), 1828
a::~~, --EtOH,
nBuCHO
87%
*
AgN03, pH 7 ,
*
a q . CH3CN,
--- -_ . _ _ _ I -
NEt3
-
reflux
RT
nBu3-O Me
86%
Chikashita, H. ; Ishimoto, N.; Kamazawa, S . ; Itoh, K . Heterocycles, ( 1985), 23, 2509 HSCH2CH2SH/SOC1 C H ( ~C H )~
4
~
~q u a n~t .
SOCl,,
aq.
.Si02
*
CH3(CH2)4<:]
SiO,
*
Kamitori, Y . ; Hojo, M. ; Masuda, R . ; Kimura, T.; Yoshida, T. J Org Chem, (1986), 51, 1427
nC6H1 3CH
/
\
SeMe
SeMe
C1 a y f e n , RT,
pentane
>
nC6H1 3CH0
90min
91 % C l a y f e n , = F e +3 / K - 1 0 C l a y Laszlo, P. ; Pennetreau, P . ; Krief, A. Tetrahedron E ,(19861, 3, 3153
66
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
n 0
0
N CS - S n - 0 - S n - N CS
Y
nCeH13CHz
f /T J
+
d i g 1 yme
,
HoH
NCS-Sn-0-Sn-NCS
I
Bu2
*
Otera, J. ; Nozaki, H.
SECTION 60A
I
Bu2
FC~H,~CHO
oooc
2h
Tetrahedron E ,(1986),
87%
3, 5743
1. BF3*0Etz
iPrCHO
t
S
‘s
S i’
/ \
Me Soderquist, J . A .
Me
CH2Cl2, 0°C
2. aq. N a F
* ; Miranda, E.I.
-
Tetrahedron Lett, (19861,
98%
3, 6305
See Section 367 (Ether - Olefin) f o r the formation of enol ethers. Many of the methods in Section 180A (Protection of Ketones) are also applicable to aldehydes.
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS
This chapter lists the conversion of functional groups into Me, CH,, Ph, etc. Et,
....,
6
-SECTION 61 : Alkyls, Methylenes, and Aryls from Acetylenes
OMe
PhCrCH, 50°C 20% H 3 P 0 4 * B F 3 25 m i n
Zinov'eva, L.V.; Ryabov, V.D.
* 0 Me
82%
J Org Chem USSR, (19841,
20,
540
Review: '!Cobalt Mediated 2+2+2 Cycloadditions: A Maturing Synthetic Strategy"
Vollhardt, K.P.C.
*
Angew Chem Int Ed w, (19841, 23, 539 ----
--
SECTION 62: Alkyls, Methylenes, and Aryls from Acid Derivatives
0"""""
Na2S208
*-IQ' \
AgNOg heat
46%
Tetrahedron E,( 1 9 8 3 , Fristad, W.E. ; Klang, J.A. 1. t B u L i , T H F , -78°C 2. P h C H 2 B r , - 7 8 O C - RT 3 . p H 3, O ° C
(10%HC1) 4. 170"C, 1 1 m m H g Muchowski, J.M.*; Solas, D.R.
*
k
H
2,2219 P
90% ~ C o u t n u n ,(19841, 2, 453
h
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
68
SECTION 64
SECTION 63: Alkyls, Methylenes, and Aryls from Alcohols and Thiols 1 . Me2C=C,
/
c1
":
0
PhCH C H C H C H = C H 2
THF' (CH~)~C=CHCH~OH 2 . PhCH2CH2MgBr, C u I
Fujisawa, Ph\C=C/ H
* T. ; I i d a ,
HMPA,
- 3 O O C
21
CH 3
+
8 6 % Ph(CH2)3CH=CHCH3 (9)
S.; Yukizaki, H . ; Sato, T.
Tetrahedron Lett, (19831, 24, 5745 Ph
H
/ 'CH20H
( 4b-e0nMzee)nPeh, M gRBT r
-
* +QOMe
reflux
(Ph3P)2NiC12
Wenkert,
(91)
* E. : Fernandes,
J.B.;
80% Michelotti, E . L . ;
Synthesis, (1983), 701
Swindell, C.S.
SECTION 64: Alkyls, Methylenes, and Aryls from Aldehydes 1 . 2 MeSeH, C H 2 C 1 2 2. n B i L i , THF, - 7 8 ° C
PhCHO
3. 4.
6
Clarembeau, M.;
t -78 - 2OoC E B u L i , THF, - 7 8 ° C * 5 . nC6H13Br Krief, A.
Tetrahedron Lett, (19861,
DCE,
NaCNBH3 20°C
0 Me
tau, J.
Ph
n6u1,
Zn12,
* C . K , ; Dufresne,
t nBu
fiCsH1 3
-4 63%
3, 1719,
1723
OMe
C.;
Bglanger, P . C . ;
J Org Chem,
51%
Pie'tre', S.; Scheigetz,
( 1 9861,
51,
3038
SECTION 68
69
ALKYLS FROM ESTERS
Related Methods: Alkyls, Methylenes, and Aryls from Ketones (Section 72)
G
SECTION 65: Alkyls, Methylenes, and Aryls from Alkyls, Methylenes, -and Aryls
1 . C B u L i , T M E D A , RT, 4 h
2. Me3SiC1
-0 -SiMe,
*
58% Andrianome, M.: Delmond, B. Tetrahedron Lett, ( 1 9851, 26, 6341
SECTION 66: Alkyls, Methylenes, and Aryls from @ides
No Additional Examples SECTION 67: Alkyls, Methylenes, and Aryls from Amines
No Additional Examples SECTION 68: Alkyls, Methylenes, and Aryls from Esters
Q
q$
f s/i 011
4
,
j
1 . CH2=CHCH2SiMe3 ZnC12, llO°C ~
2. n6u4NF ~
~
* Kozikowski, A.P. ; Sorgi, K.L.;
8-L
*HO"' (a:@=
9
3:l)
90%
Wang, B.L.; Xu, Z. Tetrahedron Lett, ( 1 983), 2, 1563
-
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
70
CH
I
0
Ii
benzene
C H 2 = C H C H - O C C F3
*
CF3COOH 80"C,
*
SECTION 68
PhCH2CH=CHCH3
8 h
78%
Fujiwara, Y. ; Kuromaru, H.; Taniguchi, H.
-J Org Chem,
OAc
[PhMe2S i 32 C u L i
i P r CI H C H = C H C H 3 T H F - E t 2 0 - p e n t a ne O"C,
(r)
2h
Fleming, I.* : Thomas, A.P.
0 OTf
( 1 9841, 49, 4309
NiC12,
*
I
SiMe2Ph
+
(r)
NaI, DMF 6 0 C ))))))
85%
* Yamashita, J. ; Inoue, Y.:
Kondo, T.; Hashimoto, H. Chem Lett, (1986), 407
--
0
(26)
iPrCH=CHCHCH3 I SiMe2Ph (74) JCS Chem Comn, (19851, 411
Zn, PPh3
CH3MgI,
(r)
iPrCHCH=CHCH3
I
3% C u C N
Et20, 0°C 60%
* 51, 2884,
Tseng, C.C.; Paisley, S.D.; Goering, H.L. ; Yen, S.-J.
, (19861,
2892
83%
SECTION 70
A L K Y L S F R O M HALIDES
71
SECTION 69: Alkyls, Methylenes, and Aryls f r o mEthers, Epoxides, and Thioethers -
The conversion ROR section.
+
RR’ (R’
CH3MgBr,
=
alkyl, aryl) is included in this
( PPh3 )
-8
iC 1
benzene, r e f l u x , 24h
t-B”
* Wenkert, E. ; Michelotti, E.L.:
t-BU
59%
Swindell, C.S.; Tingoli, M.
-J Org Chem, (19841, 9, 4894
70: Alkyls, Methylenes, and Aryls ---from Halides and SECTION Sulfonates
The replacement of halogen by alkyl or aryl groups is included in this section. For the conversion of RX + RH (X = halo) see Section 160 (Hydrides from Halides and Sulfonates).
QLBr
CoCl ( PPh3)3
\
b e n z e n e , 30 m i ?
t
c A
\
I
RT
66%
*
Momosi, D.; Iguchi, K.: Sugujama, T.: Yamada, Y Tetrahedron Lett, (19831, 24, 921 I
[ N i/ I / L i/ C
01
g l y m e , 2h
Matsumoto, H.;
* Inaba, S.; Rieke, R.D.
-J
quant
Chem, (1983), 48, 840
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
72 I
SECTION 70
PhMgBr, Pd(PPh3)4 THF, 20°C
* Widdowson, D.A. ; Zhang, Y.-A. I
7 0%
9, 2111
Tetrahedron, (1986),
-
e , P b c a t h o d e , DMF P t a n o d e , Et4NOTs t
Torii, S.
b
-
7% Pd(PPh3)4 Morisaki, K. Tetrahedron Lett, (1985),
: Tanaka, H.:
I
-
94%
26,
1655
I
PhCH2CH2ZnC1
i
5% P d ( P P h 3 ) 4
Negishi, E.
t
73%
: Matsushita, H.:
Kobayashi, M.: Rand, C.L. Tetrahedron Lett, ( 1 9831, 2, 3823
MgCl I CH2=CHC=CH2
"&,I 20% c u r , -30
*
-
, 2h
.t
- ooc
CH2=CHC=CH2
60%
*
Nunornoto, S. ; Kawakami, Y. : Yamashita, Y. J Org Chem, (1983), ---
48,
1912
A L K Y L S FROM H A L I D E S
SECTION 70
Mg Br I
73
(E)-PhCH=CHBr, DME
&OMe
*
1 % Fe(dbm)3, -20°C RT
-
RT
OMe 7 5%
Molander, G.A. ; Rahn, B.J.: Shubert, D.C.; Bonde, S.E. T e t r a h e d r o n Lett, (19831, 24, 5449
c1
H
E t M g C 1 , Et20/PhH
/H
c =c\ / \
llCsHl7
Ni(PPhg)4, 4h
RT
Ratovelomanana, V.; Linstrumelle, C. -Syn Cornnun, (19841,
(r) CH3(CH2)3CH=CHI
P h H g C 1 , LiCl
Et H
,c=c
/
H
\
"'gH1 82%
7
111, 179
CH3(CH2)3CH=CHPh C1 Rh( PPh3)3 (L) decane, HMPA 70°C 72% * Larock, R.C. ; Narayanan, K.: Hershberger, S.S. --J Org Chem, (19831, 5, 4377
*
T H F , -90°C RT, 12h
40%
Scott, F. ; Mafunda, B.G.; Normant, J.F.; Alexakis, A . Tetrahedron -Lett, (19831, 24, 5767
74
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
(L:r =
( I : &=
15:85)
SECTION 70
\
85:17)
Laycock, B.; Kitching, W.*; Wickham, G. Tetrahedron E,( 1 9831,
24,
75%
5785
I
n B u 3 S n P h , THF, 5 0 ° C 3% P d ( d b a ) 2 , 6% P P h 3 48h
Sheffy, F.K.:
Stille, J.K.
* ---J Am Chem Soc,
(1983),
105, 7173
-n.C7 H 1 5
CI
3 nC7H15MgBr NiC12(dppe) Et20, 20h, r e f l u x
CI
Eapen, K.C.:
Dua,
'C7H15
* S.S.; Tamborski, C . J Org Chem, (1984), 2, 478 ---
f l C 7 H 15 87%
1. tBuLi, pentane/Et20 -23°C
2 . HOH
* Bailey, W.F. ; Gagnier, R.P.;
Patricia, J.J. J Org Chem, (19841, 49, 2098 -
97%
SECTION 70
A L K Y L S FROM H A L I D E S
2
75
Ph
Ph
\c = c’
H
’.
(E)
H
\CH2Br
CH3CH=CHCH2SnnBu3 CH2C12,
5OoC
*
10 KBar * Yamamoto, Y. ; Muruyama, K.; Matsumoto, K. JCS Chem Comn, (19841, --TMS-CU nC6H1 3CH=CHCH2C1
6
TMPA,
*
5°C
548
(98)
n C 6 H 1 3;HCH=CH2
+ TMS
88%
87%
nC6H13CH=CHCH2THS
(2)
Smith, J.G.*: Drozda, S.E.; Petraglia, S.P.; Quinn, N.K.: Rice, E.M.; Taylor, B.S.; Viswanathan, M. J Org Chem, (19841, 3,4112 --YH3 CH3CH2CHMgC1 PdCl
, Et20
(d ppf )
OMe
OMe
75%
t
Hayashi, T. ; Konishi, M.; Kobori, Y.; Kumada, M.: Higuchi, T.; Hirotsu, K. J Am Chem Soc, (1984), 106,158
$Ih
Q ---PPh2\ PPtl2/
PdCl
CH2=CHCH20Ac,
> benzene
nBu3SnSnnBu3, r e f 1ux -
Yokoyama, Y.; Ito, S.; Takahashi, Y.: Murakami, Y. Tetrahedron Lett, (1985),
c$ 0 t
I
Ph
26, 6457
86%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
76
NiBr2(PPh3)2,
t
Otsuka, H.; Oda, Chem L e t t , (1985), 127 1 . Ni(COD),, 3 0 min . L PhCH,, R T
--
3
1
t
, HMPA RT, 2 h
*
Molander, G.A. ; Shubert, D.C. Tetrahedron
I
I
96%
* M.
* Iyoda, M. : Sakaitani, M.:
" 0
Q8 I
THF
Zn, E t 4 N I , R T , 2 h
/-SiMe, 2
SECTION 70
rSiMe3 -\o .-
77%
E,(1986), 3, 787
c B . 7! N a! O M eC 8 H 1 THF, r e f l u x 9
3% PdC12(dppf),
16h
98%
*
Miyaura, N.; Ishiyama, T.; Ichikawa, M.; Suzuki, A. Tetrahedron E , (1986), 3, 6369
Reviews: Topper Assisted Nucleophilic Substitution of Aryl Halogenf1 Lindley, J .
*
Tetrahedron, (19841, 40, 1433
"The Chemistry of Higher Order Cuprates"
Lipshutz, B.H.
* ; Wilhelm,
R.S.; Kozlowski, J.A. Tetrahedron, (19841, 40, 5005
SECTION 71
77
ALKYLS FROM H Y D R I D E S
SECTION 71 : Alkyls, Methylenes, and Aryls fr$m Hydrides
This section lists examples of the reaction RH + RR' (R,R' = alkyl or aryl). For the reaction C=CH + C=CR ( R = alkyl or aryl) see Section 209 (Olefins from Olefins). For alkylations of ketones and esters, see Section 177 (Ketones from Ketones) and Section 113 (Esters from Esters). HSiMe3, CH2=CHC02Me
S iMe3
PhH
I
>
C O ( C O ) ~ , 25°C
CH=CHC02Me
65%
3h
Takeshita, K.;
* * Seki, Y. ; Kawamoto, K.; Murai, S. ; Sonoda, N . JCS Chem Corm, (1983), 1193 --4 E C ~ H ~ ~ M ~ B ~
PhCH=CHC=CH2
I
.
OIIP ( O E t ) 2
0.1
NiC12(dppp)
Et20,
PhCH=CHC=CH2
I
RT
fiCCgH1 7
0
78%
*
Sahlberg, C.; Quader, A , ; Claesson, A. Tetrahedron E,(1 983), 24, 51 37 1. nBuLi 2 . CuBr.SMe2 3 . Me2C=CHCH2Br THF,
c r (CO) 3
-78°C 2h
- RT
>
@c r (co)3
62%
Beswick, P.J.; Leach, S.J.; Masters, N.F.; Widdowson, D.A. JCS Chem Carm, (1984), 46 ---
*
78
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
PhH,
AcOH,
100°C
*
PhCH=CHCHO Pd(02CPh)2,
3h
SECTION 71
Ph2C=CHCH0
tBu002CPh
*
Tsuji, J. ; Nagashima, H.
64%
Tetrahedron, (19841,
FeC13,
110,
2699
K-10 C l a y
PhH,
4OoC,
5h 65%
Chalais, SA; Cornelis, A . ; Gerstmans, A.; Kolodziejski, W.; Laszlo, P. ; Mathy, A.; Metra, P. Helv Chim Acta, ( 1985), 68, 1 196 --NO
CH2=CHPh Pd(dba)2, 40°C,
Kikukawa,
* K. ; Naritomi,
*
CH3CN
.
*
.. 60%
4 0 rnin l 3 \
\ J /
Ph
M.; He, G.-X.: Wada, F.: Matsuda, T. Chem, (1985), 50, 299
J Org -
Ishibashi, H. ; Nakatani, H.: Umei, Y.: Ikeda, M. Tetrahedron Lett, ( 19851,
-
26,
4373
SECTION 72
79
A L K Y L S FROM KETONES
SECTION 72: Alkyls, Methylenes, and Aryls from Ketones
-
The conversions R,CO this section. M e O y o M e
+
RR, R,CH,, R,CHR', etc. are listed in
'
fiBuLi
OMe
2 . MeTiC13 Me2TiC1
*
J Org Chem, (1983),
Reetz, M.T. ; Westermann, J. S
II
P214,
PhH,
reflux
6h
Suzuki , H.*;
Tamano, M.;
85%
Tani , H. ; Takeuchi , S.
--will Chem Soc *,(19851, 58,
& 0
254
PhCH P h
t
PhCPh
48,
1 . 2 PhPH2,
140°C
sealed tube, 2.
EtSSEt,
3d
140°C
sealed tube,
Jf*Jc-
I d
2421
/
\
dD 91 %
* --Koketsu, J. B u l l Chem Soc Jpn, (1985), 58,
b-+ NNHTRIS
*
1. 2 LBuLi, O O C ,
2.
D20,
THF
15 min 0°C
Chamberlin, A.R. ; Bloom, S.H.
t
Tetrahedron Lett, (1986),
2577
H
87%
3, 551
6
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
80
\
OMe
SECTION 74
P214
LiA1H4/
PhH, N2, r e f l u x
>
6h
0 OMe
Suzuki, H.* ; Masuda, R.; Kubota, H.: Osuka, A.
-Chem Lett,
65%
(19831, 909
Pt02, EtOH 48h
H,,
L
81 %
* * Subramanian, L.R. ; Garcia Martinez, A. : Herrera Fernandez, A.;
Martinez Alvarez, R.
Synthesis, ( 19841, 481
SECTION 73: Alkyls, Methylenes, and Aryls from Nitriles
-
MeBPh3-Me4Nf \
\
CN
Lan, J.Y.;
CH3CN
, hv
* Schuster, G.B.
(1 .25
: quant.
Tetrahedron Lett, (1986),
1)
3, 4261
SECTION 74: Alkyls, Methylenes, and kyls from Olefins
-
-
-
The following reaction types are included in this section: A. Hydrogenation of Olefins (and Aryls). B. Formation of Aryls. C. Alkylations and Arylations of Olefins. D. Conjugate Reduction of Conjugated Aldehydes, Ketones, Acids, Esters, and Nitriles.
SECTION 74A
81
H Y D R OGENATI ON
E. Conjugate Alkylations.
F. Cyclopropanations, including halocyclopropanations. SECTION 74A: Hydrogenation of Olefins (and Aryls)
Reduction of aryls to dienes are listed in Section 377 (Olefin Olefin).
* Alper, H. ; Heveling, J.
r x
H2,
97 %
JCS Chem Comn, ---
(1983), 365
P H 7.6, R T
[ 1 , 5 HDRhC1I2, 1 a t m nBu4NHS04
97%
*
Januszkiewicz, K.R.: Alper, H. Organometallics, (1 9831,2, 1055
-0
- IB F4
[: R h ( N B D ) ( d i p h o s 4 800 p s i H 2 ,
A Evans, D . A .
25°C
THF/HOH
* : Morrissey, M.M.
---J Am Chem
“’0H
A H
Soc, (19841,
95%
106,3866
82
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
[1 ,5 H D R h C 1 I 2 , R T
Br(CH2)4CH=CH2 Januszkiewicz, K.R.:
*
'gH1 4 ' pH 7 . 6 , 4 h 1 atm H2
* Alper, H.
SECTION 74A
Br(CH2)5CH3 78%
--C a n J Chem, (19841, 62, 1031
[ (04PhqC4CO) (C02 ) R u 1 2
CH3(CH2)5CH=CH2
autoclave, 145OC
500 p s i H 2 ,
10 m i n
t
CH3 (CH2)gCH3 quant.
*
B l u m , Y.: Czarkie, D.: Rahamim, Y.: Shvo, Y. Organometallics, ( 1 985 1 , 4, 1 459
*
Crabtree, R.H. ; Davis, M.W.
J Org Chem, (1986),
N a H , L A m O N a , Ni(OAc)2 M e 3 S i C 1 , D M E , 4 5 O C , 4h
* Tetrahedron Lett,
Fort, Y.: Vanderesse, R.; Caubere, P. Review:
51,
2655
*o
99%
( 1 9861,
3, 5487
"G-Akyl and cis-Acylrhodium and Iridium Hydrides: Model Intermediates in Homogeneous Catalysis"
Milstein, D.
*
Accts Chem Res, ---
(19841,
17,221
ALKYLATIONS
SECTION 74C
83
SECTION 74B: Dehydrogenation to form Aryls
No Additional Examples SECTION
E: Alkylations and Arylations of Olefins
PhCH=CHCH2NMe2
Richey Jr., H.G.
1, nBuLi , hexane r e f l u x , 6h
2 . MeOH
* ; Heyn,
>
I
PhCH2kHCH2NMe2
W.F.
A.S.; Erickson,
J Org C h m , (1983), ---
MgEt2,
52%
48,
3821
Et2OY 2coc
C H ~ ( C H ~ ) ~ C H = C H ~ Cp2ZrC12,
Dzhernilev, U.M.:
nB u -
. )
l h
CH3(CH
) CHCH3
3t
Et
Vostrikova, O.S.; Sultanov, R.M. B u l l Acad Sci USSR, (19831, ----
93%
32, 193
\ 2 A1C13, CH2C12,
-78°C
3 rnin
61 %
*
Trost, B.M. ; Ghadiri, M.R.
2 Am
-
Chem Soc, (1984), 106, 7260
84
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION E: Conjugate Reductions 20% [Ir(COD)Py(PCy3)]PF6
L 5
H2(homogeneous),
0
Stork, G.*:
Kahne, D.E.
H2,
n Ph NHAc
J Am Chem Soc, ----
40 Bar
1 2 h,
9.
*
RT
-6 0
k (L:E = 96:4) (1983), 105,1072
MeOH
-COOH Ph
/
LH s
N
y
Ph
Angeu Chem Int Ed Engl, (1984),
L a N i 5H6, -78
-
23, 435
*
*
Inamoto, T. ; Mita, T.; Yokoyama, M. JCS Chem hum, (19841, 163 --H 0
m:;CHPh,
II
Me2C=CHCCH3 A1C13,
MeOH,
80°C
*
NHA~ qudnt.
(99% ee)
THF/MeOH 0°C
90%
H
*
pPh3
Ph,p - ?
Nagel, U.
CH2C12
RT, 2 4 h
SECTION 74D
f0 89%
0
II ,I
Me2CHCH2CCH3
24h
sealed tube * Chikashita, H. : Miyazaki, M.: Itoh, K.
76%
Synthesis, (19841, 308
SECTION 74D
CONJUGATE REDUCTIONS
6
To I
9 8 % HC02H,
* Yoneda, F. ; Kuroda, K.;
120°C,
85
25h 81 %
Tanaka, K.
JCS Chem C a m , ---
(19841, 1194
H ~ P O ~ - / H O H ,2 o o c 1 0 % Pd/C,
90%
EtOH/HOH
CHO
30 m i n
*
Sala, R. ; Doria, G.; Passarotti, C. Tetrahedron L e t t , ( 1 9841, PhCH=CHC02Et
(E)
( PPh3)3RhC1,
RT
Et3SiH,
8h
*
Liu, H.-J. ; Ramani, B. ,NHAc
polymer
-
PhH,
*
Carmun, (19851,
I Rh - p o l y m e r
25, 4565
PhCH2CH2C02Et 98%
3,965 /NHAc
(64% ee S ) 2 , 2 - 0- i s o p r o p y l i d e n e - 2 , 3 - d i h y d r o x y - 1 , 4 e(dipheny1phosphino)butane
Deschenaux, R.; Stille, J.K.
* -J Org Chem,
(19851,
50, 2299
86
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 74E
H a,"rCHPh H
*
PhCH=CHN02
nBuOH, r e f 1 u x
PhCH2CH2N02 88%
l h
*
Chikashita, H. ; Morita, Y.: Itoh, K. Syn Cornnun,
2.5
(1985), 15, 527
Ph2SiH2
0 . 3 5 ZnC12 2% Pd(PPh3l4
*
CHC13,
2h
Keinan, E. ; Greenspoon, N. /C02Me
CH2=C
\
Me
1 . Mg,
26,
Tetrahedron E ,(1985),
FleOH,
2 . 3N HC1,
96%
10°C,
2h
O°C
3 . 3N NH40H
Youn, I.K.; Yon, G.H.; Pak, C.S.
*
Me2CHC02Me
80%
*
Tetrahedron
e, (1 986 ' -27, 2409
SECTION 743: Conjugate Alkylations 0
it
Ke2C=CHCCH3
1 . A1 ( S i M e 3 ) 3 2 . MeOH 3. A1(SiMe3)3, 4 . MeOH
* Altnau, G. ; Rejsch, L.
1353
Me3Si t -78°C
Tetrahedron
\
0
It
Me2CCH2CCH3 75%
E, (19831, 2,45
CH2=CHCH2SiMe3
.
PhCH=CHC02Me
(L)
87
CONJUGATE A L K Y L A T I O N S
SECTION 74E
CH2C02Me
nBu4NF
*
I
PhCHCH2CH=CH2
H M P A / DM F
90%
*
Majetich, G. ; Casares, A . M . ; Chapman, D.: Behnke, M. Tetrahedron Lett, (19831, 2,1909
-
nBudNF,
RT,
l h
63%
*
Majetich, G. ; Desmond, R.; Casares, A.M. Tetrahedron Lett, (19831,
0
0 Et02CCH2C02Et, DBN,
15 KBar,
25°C CH3CN I
48h
Dauben, W.G.*; Gerdes, J . M .
I(CH2)4
c‘
Me
2, 1913
‘C02tBu
Cooke J r . , M . P .
C02Et
Tetrahedron Lett, (19831,
1. nBuLi, TH F
=c
’
60%
- 1 O O O C
2,3841 C02tBu
2 . EtOH
* -J Org
86%
, (1984), 9, 1144
88
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
b
SECTION 74E
EtA1C12
( C H2 ' 3 3
t a
PhCH3 -78°C
I
Me3S i
Schinzer, D.
*
+
H
(7.5
1) 70%
Angew Chem I n t Ed Engl, (1984), 23, 308
-0
1 . He211g, DMF, - 7 8 O C 18-crown-6
2. Al/Hg
'h,
%,
69%
Posner, G.H.
* : Hulce,
M.
PhCH21,
(97% ee)
Tetrahedron L e t t , ( 1 9841,
flBu3GeH
CH2=CHCN
Pike, P.;
.t
A I B N , PhH, 1 2 h r e f 1ux Hershberger, S.: Hershberger, J.
383
Ph(CH2)3CN 76%
*
Tetrahedron L e t t , (19851,
1.
25, 379,
26, 6289
iPrCu.BF3 TH F
2.
2 N KOH MeOH
i-Pr
H
&COO" (2)
Helmchen, G.*: Wegner, G.
97%
Tetrahedron Lett, (1985),
26, 6051
SECTION 74E
89
CONJUGATE A L K Y L A T I O N S
1. 2
iI
Bu2Cu*BF3, E t 2 0
B u L i - C u I , -78OC P B u ~ / B F. O~E t 2 Et20/THF,
2.
NaOH,
* Oppolzer, W. ; Dudfield, P.;
-78°C
aq. EtOH
r e f 1u x
(95% ee)
Stevenson, T.; Godel, T.
Helv Chim Acta, ---
1 . PhCu*BF3, E t 2 0 - 7 8 - -2OOC
(19851,
+
2. Ac20,
DMAP
3 . TsOH,
aq. acetone
68, 212,
216
*
CH3CHCH2CH0
I
Ph
70%
( 7 3 % ee S )
I
* Normant, J.F.
Mangeney, P.: Alexakis, A,: Tetrahedron Lett, ( 1 9861,
-
3, 31 43
iPrBr, Zn/CuI aq. EtOH 18OC,
45 m i n
*
94%
Petrier, C.; Dupuy, C.; Luche, J.L. Tetrahedron Lett, (19861, 3, 3149 de Souza Barboza. J.C.: Petrier, C.; Luche, J.-L. Tetrahedron Lett, (19851, 26, 829 CH =C
/
C O Me
2
1 . EtMgC1, 5%
CUI,
2. H30t
Et20/PhH 0°C
s
,C02Me CH3CH2CH2CH 'NHA~
80%
Cardellicchio, C.; Fiandanese, V.: Marchese, G.: N~so,F.* Ronzini, L. Tetrahedron Lett, (19851, 26, 4387
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
90
SECTION 74E
1. PhLi T OC’
2.
O
j
CH31
3 . a q . NaHC03
PPh,
*
Tetrahedron E ,( 1985),
+
1 . PhN2 B F 4
-,
HOH
TiCl 2. NaOH/acetone 5°C
* Citterio, A. ; Cominelli, A.; 1
-eN H“ COOH
2.
*
&N-
nBu 0
so2
2.
=
,COOH CH
I
+
“QCOOH 68%
Bonavoglia, F.
nB u
nBuLi
( - ) Spar te ine 6M H 2 S 0 4
-1
*
P hCHCH 2 C O O H
41 % ( 5 7 % ee R )
JCS Perkin I, (1986), 759
1. L~BH(=-BU)~
1
Ph,
Ac OH
Soai, K. ; Ookawa, A. - -R
26, 3079
Synthesis, (19861, 308
q
Ph
93%
(30:l)
Liebeskind, L.S. ; Welker, M.E.
MeI/HMPA
--Bu
-
+y 0
(99)
:
+ :
64%
RYYBu
R
Oppolzer, W. * ; Poli, G.
R
(11
Tetrahedron=,
(19861, 3, 4717
SECTION 74E
Q Q
1.
PhGN-NMe, - Me HO
2.
Me1
3. CuI,
4.
*
91
CONJUGATE A L K Y L A T I O N S
,
EtLi
THF-SMe2
EtLi
90%
5 . Me1
(92% ee R )
Corey, E.J. ; Naef, R.: Hannon, F.J. ---J Am Chan Soc, (19861, 108,7114 1 . ZnC12.TMEDA, _.
nBuMg C l
2. aq.
w
NH4CI
t
Kjonaas, R.A. ; Vawter, E.J.
Lipshutz, B.H.
THF
96%
J Org Chem, (1986),2,3993
* : Wilhelm, R.S.:
Kozlowski, J.A. J Org Chem, (1984), 2, 3938
1
*
Lipshutz, B.H. ; Parker, D.A.: Nguyen, S.L. ; McCarthy, K.E.; Barton, J.C.: Whitney, S.E.: Kotsuki, H. Tetrahedron, (19861, 2, 2873
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
92
SECTION 74F
Reviews: IIThe Chemistry of Higher Order Cupratesf'
* : Wilhelrn,
Lipshutz, B.H.
R.S.: Kozlowski, J . A .
Tetrahedron, (1984),
40,
5005
"Selective Synthesis by Use of Lewis Acids i n the Presence of Organocopper and Related Reagents"
Yamamoto, Y .
*
Angew Chem Int Ed Engl, (1986),
3,947
SECTION 74F: Cyclopropanations
'I
c0 * R
Me2C=PPh3 THF,
R 0,c
,,&
-78°C
* qCOpR (13
R = menthyl de Vos, M.J.;
Ando, R . ;
+
M'
COpR
""C0,R
87 ) (74% ee)
* Krief,A.
-
Tetrahedron Lett, (19831,
* JCS Chem Comn, ---
Sugawara, T.; Kuwajima, I.
85%
2,103
64%
(1983), 1514
1. nBu3SnLi
Fleming,
2.
PhMgBr
3.
B F 3 * 2 AcOH
* I. ; Urch,
* 48%
C.J.
Tetrahedron=,
(19831, 24, 4591
SECTION 74F
93
CYCLOPROPANATIONS
3. PhH, reflux CuS04, C u ( a c a c ) 2 24h
*
50%
Hudlicky, T. ; Reddy, D.B.: Govindan, S.V.; Kulp, T . ; S t i l l , B.: S h e t h , J.P. J Org Chem, (19831, 48, 3423
-
CH2=C
N 2 C P h 2 , hv E t 2 0 , 25°C
/C N
‘OAc Oku, A , * ;
8h Yokoyama, T.:
* 70%
Harada, T. -J Org Chem, (1983),
48,
5333
Cp(C0)2FeCH(OMe)Me
2
Me3SiOTf , C H 2 C 1 -78°C
Brookhart, M.*:
*
Tucker, J . R . ; Husk, G.R. J Am Chem Soc, (1983), ----
N2CHC02Et, 2 2 ° C CH CH=CH2 1 2
CH2CH=CH2
*
R h ( O A c ) 4 , 4h
86%
105, 258 (C&)2CH=CH2
C02Et 80%
Anciaux, A.J.; Gemonceau, A . ; Noels, A.F.: Warin, R.: Hubert, A.J.:
T e y s s i e , P.
Tetrahedron, (1983),
3,2169
94
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
8
(
B
SECTION 74F
a N*SbCIi
r
N2CHC02Et,
CH2C12
15 min
O O C ,
*
67%
Stufflebeme, G.: Lorenz, K.T.: Bauld, N.L. J Am Chem Soc, ( 1 9 8 6 ) , ----
/ I , _
108,4234 it.,
V "
(E:I=
Pazynina, G.V.; Luk'yanets, E.A.; Bolesov, I . G . J Org Chem USSR, ( 1 9 8 4 ) , ---Pd(OAc)2 c a t a l y s t ,
PhH,
40°C
Majchrzak, M.W.*; Kotelko, A.: Lambert, J . B . Synthesis, (1 9 8 3 ) , 469
7
OSiMe,
CHBr3,
pentane,
*
2 CH2=CH
\
C02Me
.
*
R T , 2h
20,
b2
2.
J Am Chem Soc, ----
1731 76%
= 1:2)
82%
Rousseau, G . ; Slougui, N. 1. 2
20°C
1.2:l)
oa
(E:Z - -
Et2Zn,
quant.
C02Et
(1984), 106, 7283
, P h H , 80°C
a q . THF, 25OC
..
AcOH
69% ( Z_ : E-
= 95:l)
Boger , D L. *; Brotherton, C E Tetrahedron Lett, (19841,
25, 5611
SECTION 74F
95
CYCLOPROPANATIONS
1 . L D A , THF,
-30°C
-
2. C l ~ S e ( O ) C H = C H ,
Ph
-
-3OOC
RT
72%
* I.
Ando, R.: Sugawara, T.; Shimizu, M.: Kuwajima, Bull Chem Soc *,(19841,
---
N2CHC02Et,
25°C
*
8h
,C02We EtCH=C
\
C02Me
2897
@
C02Et
0.5% Rh2(OAc)q
Doyle, M.P. *: Dorow, R.L. W.H.: Trudell, M.L.
57,
:
(E:L
= 2.1:l)
96%
Buhro, W .E. Griffin, J.H. ; Tamblyn, Organauetallics, (1984),
2, 44
1. Me2C(Li)S02Ph THF,
20"C,
2 . MeOH,
30 min
C02Me
70°C
3 . H30+
*
Krief, A . ; de Vos, M . J .
64%
Tetrahedron E,(19851,
26, 61 15
0 Ph2P,I1
,CH2CH20H CH
tBuOK/tBuOH
1
0bCPh
Wallace, P.: Warren, S.
~
$Ph
3OoC, 2 h
*
qua n t
Tetrahedron E,(19851,
.
26, 5713
96
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
iBu3Al,
SECTION 74F
CH212
hexane
Maruoka, K.: Fukutani, Y.: Yamamoto, H. -J org Chem, (1985),
-
2 CH2Br2, cat.
Friedrich, E.C. 0 II
73%
3,4412
4 Zn
CuC1,
E t 2 0 , 45°C
* : Domek, J.M.:
-J Org
+
Pong, R.Y.
60%
Chem, (1985),
50,
*
Ph
4640
Ph3P-CH2Ph KF-A1 * 0 3
PhCH =CHC P h
70"C,
*
24h
(L:L=
0
1:1)
Texier-Boullet, F. ; Villemin, D.: Ricard, M.: Moison, H.; Foucaud, A.
72%
SECTION 75 Review:
Murai,
97
A L K Y L S FROM M I S C .
ffSiloxyCyclopropanes: Useful Synthetic Intermediates" S.*;
R y u , I.; Sonoda, N. -J Organomet
e, (1983),
250,
121
SECTION 75: Alkyls, Methylenes, and Aryls from Miscellaneous
-
0
compounds
OP(0)[OEt12
PhMe2Si .A1 E t 2 THF, 0 - 25OC
-0 Si Me,Ph
Okuda, Y.: Sato, M.; Oshima, K.: Nozaki, H. Tetrahedron Lett, (19831, 2 L i n-B u 3 B H ,
THF
PhS02Ph r e f l u x , 2h
*
*
Ph (CH2) 3CH3
Brown, H.C. ; Kim, S.-C.: Krishnamurthy, S. Organometallics, ( 1 983),
6
N-NHCPh2tBu
1 . LDA,
24, 2015
7 9%
2,
PhCH2Br
*
2 . PhSH
7 9%
Baldwin, J.C.*; Adlington, R.M.; Newington, I.M. JCS Chem Cam, (19861, 176 ---
779
dh 71%
Reviews:
"Copper(1) Catalyzed Reactions of Organolithiums and Grigard Reagents" Erdik, E.
*
-
Tetrahedron, (19841, 40, 641
"Syntheses with Radicals: C-C Bond Formation via Organotin and Organornercury Compounds" Giese, B.
*
Angew Chem Int Ed
x, (1985),
2, 553
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 6 PREPARATION OF AMIDES
--
SECTION 76: Amides from Acetylenes
No Additional Examples SECTION 77: --Amides from Acid Derivatives
exylene, 3h
Ph(CH2)3COOH
* Mukaiyama, T. ; Ichikawa, J.; 1
.
Chem Lett, (19831, 683
fy&
M e 0 a X M g B r
PhSCH2N3, E t 2 0
Me0 ~
'
\
OJ 0
7 5%
*
Trost, B.M. ; Pearson, W.W.
COOH
86%
Asami, M.
- TO H ,F 0°C 2 . MeOH aq. K
nC5H1
*
ref1 ux PhCH2CH2CH2NH2
0 II Ph(CH2)3CNHCH2CH2Ph
J Am C h m ----
P y , RT, l h 2.
P h N H 2 , 2h
Ueda, M.*: Oikawa, H.: Teshirogi, J.
Soc, (1983),
*
105,
"C5H1
1054
iiCNHPh 66%
Synthesis, (1983), 908
SECTION 77
Cabre', J.; Palmo, A.L.
*
Synthesis, (19841, 413 24h
N3CH2CH2iPr, CH3CH2COOH
99
A M I D E S FROM A C I D S
PPh3,
PhH,
0
II
Pr CH 3 C H 2 i N H C H 2 C H 2i
reflux
*
88%
Garcia, J.: U r p i , F.: Vilarrasa, J. Tetrahedron E ,(1984), PhCH2NH2,
Py
25, 4841 0
II
*
PhCOOH
PhCNH P h 95%
*
Ueda, M. ; Kawaharasaki , N. : Imai , Y. Bull Chem Soc Jpn, (1984) , ----
-
0
*
PhCH2NH2,
K i m , S. ; K i m , S.S.
RT,
85
0
a-o!(OPh)2 PhCH2COOH
57,
,
CH2C1
NEt3
0
II
t PhCH2CNHCH2Ph
30 m i n
JCS Chem Carm, (1986), 719
Related Methods: Amides from Amines (Section 82)
85%
100
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 81
SECTION 78: Amides from Alcohols and Thiols
--
No Additional Examples
Ho
SECTION 79: Amides from Aldehydes
- --
PPh3,
n C 7 H 1 5CH0
PhBr,
, P ~ ( O A C ) ~ K 2 C 0 3 , DMP
r e f l u x , 24h
*
Tamaru, Y.; Yamada, Y.; Yoshida, Z. 1. LiN(SiMe3)2, 2.
Me3SiC1,
PhCHO 3 * Me2C=C,
Et,O L
4. LBuOH
THF,
30 m i n
,OM e OTMS'
U
59%
Synthesis, (19831, 474 0°C
*
Znr2
5. 3 ReMgBr
Colvin, E.W.": McGarry, D.G.
; i n0
nC7H15C-N -
60%
JCS Chem Cam, (1985), 539
SECTION 80: Amides from Alkyl, Methylenes, and Aryls
- --
No Additional Examples SECTION
81: Amides
from Amides
Conjugate reductions of unsaturated amides are listed in Section 74d (Alkyls from Olefins).
A M I D E S FROM A M I D E S
SECTION 81
&\
*
mc p b a
101
&+ Y
Me
J!
Me
72%
Kochhar, K.S. ; Cottrell, D.A. : Pinnick, H.W.* Tetrahedron E ,(19831, 24, 1323
Q
. )
2. n B u 3 S n C H 2 C H = C H 2 AIBN, PhCH3
Webb 11, R.R.;
*
Danishefsky, S. Tetrahedron Lett, (19831,
-
1 . C0Cl2, HC1
0
2. P h C H = N P h , N E t 3
!I
Me2CHCNMe2
82%
3. a q . KC104
4. a q . K O H - C H 2 C 1 2
\s: 2,1357
- -DPh ‘Ph
86%
Magchand-Brynaert, J.: Moya-Portuguez, M.: Huber, I.: Ghosez, L. JCS Chem Comn, ( 1 9 8 3 , 818 ---
*
Watanabe, Y. ; Ohta, T.: Tsuji, Y. Bull Chem Soc
--- s,(19831, 56,
2647
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
102
Yamamoto,
* T. ; Kurata,
Bn
Himstra,
quant.
Chem, (19831, 61, 86
THF, -78°C
1. LDA,
OO O r E t
Can J ---
Y.
2. Z-ICH2CH2CH=CHEt
-78 - O°C 3. C F 3 C O O H , S n C 1 4 , R T W.J.:
/
0 HII-Bu a p
I
Speckamp, W.N.
- dPh
CH3CN, l h
* A . ; Terao,
PhH,
77%
Chem, (1984), 49, 1149 -J Org -
P h S e C l , RT
Me
Bn
CH2C12, 21h
* H. ; Klaver,
Toshirnitsu,
SECTION 81
N;-B”
94%
Uernura, S. Tetrahedron Lett, (19841,
K.;
-
25, 591 7
r
Thornsen, I.: Clausen, K . ;
quan t .
Scheibye, S.: Lawesson, S.-0. Org Syn, (1984), 62, 158
*
SECTION 81
6 0,
AMIDES FROM A M I D E S 1. nBuLi
Ni-Pr2
Sharp, M.J.:
103
2 . B(OMe)3 Ht
3.
4 . Pd(PPh3)4,
* Snieckus, V.
-)r $
PhO2S N
PhBr
82%
Tetrahedron E ,(1985),
26,
nBu3SnH, AIBN PhH,
reflux,
10h
Br
Padwa, A. * : Nimmesgern, H.; Wong, G.S.K.
O0 H
1 . e - , MeOH 2 . C1CH20Me,
NaH
4. H2,
TiC14 N i ( R ) , KOH
Uchida, K.; Kobayashi, H.
J Org
Chem, ( 1 985) ,
Me3SiCl,
ILtJ 0
Lt
3 . CH2=CHCH2SiMe3
* Shono, T. ; Matsumura, Y.;
84%
ZnC12,
50,
NEt3
31 %
3243 C0,Et
PhCH3
185OC,
0
7h
56%
*
Ihara, M.; Kirihara, T.; Fukmoto, K. ; Kametani, T. Heterocycles, (1 985),
23, 1097
5997
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
104
S
,
I!
KO2
PhCNHnPr
*
CH3CN, - 3 5 ° C 5h
K i m , Y.H. ; Chung, B.C.;
Chang, H.S.
-
Tetrahedron Lett, ( 1 985) , 26, 1079 c1 I C H 3 C H C H 2 C H 3 , DMF
+
e , Pt electrode E t 4 N O T s , RT
Shono,
P h C N H-n P r
92%
-
H
>
SECTION 82
* T. ; Kashimura,
NaguSa, H.
S.;
A/ 68
Chem Lett, (1986),
425
SECTION 82: h i d e s from Amines
- ---
"' I
t-BU
Alper,
20 a t m CO,
H. * ; Urso, F.;
n /"\o -
Me
Ph
, 90°C PhH
t-BU
quant. Smith, D.J.H.
J Am Chem ----
Soc, (1983) ,
9,6737
1. JBuMe2SiOSO2CF3
CH2C12,
0°C
2. M e L i , T H F , P h C C l II 0 ° C - RT 0
&Ph
76%
Okazaki, R.*:
Takitoh, N.
JCS Chan Cum, ---
(19841, 192
%
SECTION 82
8
AMIDES FROM AMINES
tBuMe2SiC1
(L)
, DMF
N E t 3 , 4 O o C , 10h 4-DMAP
H
,C02Me PhCH2CH \NH2*HC1
*% Me0
Me0
Djurii, S.W.*
105
-J
N
CHO
78%
aChem, (1984), 49, 1311
n
1 . C1 3 C C H 0 , M e N U0 ,C02Me ether PhCH2CH 2 . Mg(C104)2-2HOH \ NHCHO D M F , RT 77%
*
Giesemann, G. ; Ugi, I.
Synthesis, (1983), 788
- v0
4 5 atm CO ZnEt2, 100°C 18h
H
Yoshida,
* Y. ; Asano,
S.:
Inoue, S. 2 y
CH3(CH2)7NH2
co
1 8 0 ° C , P h H , 6h
CHO 80%
Chem Lett, (1984), 1073
*
CH~(CH~)~NHCHO
*
91 %
Tsuji, Y.: Ohsumi, T.: Kondo, T.; Watanabe, Y. -J Organomet (1986) , 309, 333
e,
Related Methods: h i d e s from Carboxylic Acids (Section 77) Protection of Amines (Section 105A)
106
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 84
SECTION 83: Amides from Esters
---
HMPA 220"C,
m-BU
> 5h 54%
a Carmun,
Gupton, J.T.; Baran, D.; Bennett, R.: Hertel, G.R.; Idoux, J.P. 1. LDA,
(19841, 14, 7001
2 . BnNHCH2CN,
-
-70°C 3.
tL"
-7OOC
TH F- h e x a n e
Me2CHC02Et
20h
*
0
RT
a q . NH4C1
Overman, L.E. * ; Osawa, T.
THF/DMSO, NaNHTs,
66%
J Am Chem Soc, (19851,
5% Pd(PPh3)4,
*
107,
1698
TsNH2 50°C
22h
*
Bystrljrn, S.E.; Aslanian, R.: BBckvall, J.-E. Tetrahedron Lett, (1985),
SECTION ---84: Amides fran Ethers, Epoxides,
7 5%
26, 1749
and Thioethers
No Additional Examples
A M I D E S FROM H A L I D E S
SECTION 85
SECTION
85: h i d e s
CH2=C
2. CO,
1
\
CH,Br L
Mori,
and Sulfonates
f m m Halides
1. BnNH2,
Br
K2C03
NBu3,
100°C
Bn
8% Pd(OAc)2-PPh3
3. H2,
* M. ; Chiba,
K.:
Pt02
58%
Okita, M.: Kayo, I.; Ban, Y. Tetrahedron, (1985), 375
41,
1 . FleSiNEt2, DMF
Ph
3 N i ( C 0 ) 4 , 70°C 2 . HOH
Hirao, T.
107
* ; Nagata,
*
0
I1
VCNEt 85%
S.; Yamana, Y.:
Agawa, T. Tetrahedron E,(1985),
26,
5061
0 u I'I r
rn
N i ( C 0 ) 4 , 70°C
V
* T. ; Harano,
Hirao, Agawa, T.
tBuN=C=O
V
63% Y.;
Yamana, Y . ;
Hamada, Y . :
---B u l l Chem Soc Jpn, RT, 4 5 rnin 2 . Na, THF-HMPA
3. H30
Einhorn, J.;
rhiun
*
Nagata, S.:
( 1 986),
59,
PhCNH t B u
-I.
* Luche, J.L.
1341
78% Tetrahedron Lett, (1986),
3,501
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
108
SECTION 87
SECTION 86: -Amides from Hydrides No Additional Examples SECTION 87: Amides from Ketones
---
1 . Fp(Me2C=CH2)PF CI H 2 C H = C H 2
I
CH2CC02Me
It
0
CH2Cl
2. NH3,
6
*
CH2C12
3 . NaBH4,
MeOH
4 . CH3CN,
65OC
5. Ag20,
THF,
( -E : _Z
RT
=
2:l)
* 11% o v e r a l l Berryhill, S.R.; Price, T.: Rosenblum, M. J Org Chem, (19831, 48, 158 0 II
2 NaN3,
EtOH
reflux,
10h
NH-COEt
Br
Br
*
43%
Weber, G.: Hauptmann, S . : Wilde, H.: Mann, G. Synthesis, ( 1983), 191 1 . NH2-OS03H 9 5 % HCOOH, 2.
Olah, G.A.*;
HOH,
Fung, A.P.
pH 7,
, 3h reflux RT
Org Syn, (1984),
9,188
63%
SECTION 88
A M I D E S FROM N I T R I L E S
W?ilchli, R.; Bienz, S.:
Hesse, M. Helv Chim Acta, (19851, ---
SECTION
*
68,
484
88: hides from Nitriles 1 . LBuBr,
0
K-10 c l a y
FeN03,
EtCN
CH3CN,
*
RT
2 . HOH
w i t h 3" h a l i d e s o n l y Y Polla, E. Bull Chem Soc Belg, (19851,
----
1. LiA1(OEt)3H, PhCN
109
Et20,
35%
2, 81
0°C
2 . M e 3 S i C 1 , 0°C - RT w 3 . Me2C=C-OLi , -78 - -30°C I
4.
O"C,
I1
Et CNHtB u
OEt a q N H C1
b: 0
57%
Andreoli , P. ; Cainelli, G.!; Contento, M. : Giacomini , D.; Martelli, G.; Panunzio, M." Tetrahedron E,(19861, 3, 1695 Pip, CH3CN
2 HOH,
DMF,
160°C
sealed tube
3% RuH2(PPh3)4,
Murahashi, S.-I.
* ; Naota, T.:
24h
Saito, E.
J Am Chem Soc, ----
2
97%
(19861,
108,7846
110
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 89
- --
SECTION 89: Amides fruu Olefins
NaBH4, aq.
BuNH2, NaOH
w
Barluenga, J . ; Jirngnez, C.;
v
0°C
92%
Ngjera, C.; Yus, M. I , (1 9 8 3 , 591
JCS P e r k i n ---
1 . R-NH2,
CH2C12,
Hg(NO3I2,
reflux
2 . NaBH4, BuNH2, a q . NaOH
-a
24h
0°C
-
I
R
R = C02Me
96% w
-J Heterocyclic e, (1983), 20,
Barluenga, J . ; Jirnenez, C . ; Najera, C . ; Yus, M. R = Ts
Barluenga, J.
/
1733
6 3Z w
;
Jirngnez, C . ; Nije'ra, C.: Yus, M. JCS P e r k i n I , (1984), 721 ---
C
*
Bloom, A . J . ; Fleischmann, M.; Mellor, J.M. JCS P e r k i n I , ( 1984), 2357 ---
84%
SECTION 90
111
A M I D E S FROM M I S C .
SECTION 90: Amides from Miscellaneous Compounds
--
1 . Me2C=C:
OMe
,OTMS
I
3.
Shono,
* T. ; Tsubata,
NO2 I
RMgBr,
,
TiC14
-J O r g Chem,
(19841, 49, 1056
4 A c O H , 1 % PtCl,(PPh,),, L 1 0 % SnCl,, 180°C
* Y . ; Tsuji, Y.:
7 1("
6 5%
0°C
THF,
Okinaga, N.
K.;
dioxane,
Watanabe,
OMe
J
NHAc
L
*
60 atm CO
4h
91 %
Kondo, T.; Takeuchi, R.
--J Org
9, 4451
Chem, (19841,
1. n B u L i , -78"C, THF 2. E PhCHZNPh, - 7 8 ° C
*
oC\\>\\l\jFe PPh,
3.
MeOH
4.
CAN
Broadley, K . ; Davies, S.G.
'"'P h
*
no y i e l d Tetrahedron Lett, (1984), 25°C
1 . 3 BnFIH2, 48h
2. Br2/NEt3,
*
Ojima, I. ; Kwon, H.B.
nPh
0
-Chem Lett,
-78°C
(19851,
reported
2, 1743
4f
1327
Bn
56%
112
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 90
Reviews : "Synthesis and Reactions of Sulfamidesff McDermott, S.D.; Spillane, W.J. Org Prep Proc Int, (19841, llcr-Arnide Alkylation a t Carbon: Recent Advances" Zaugg, H.E.
*
Synthesis, (1984), 85, 181
5, 49
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 7 PREPARATION OF AMINES
SECTION 91: --Amines from Acetylenes No Additional Examples
6'' SECTION
92: Amines
from Acid Derivatives
1 . NaN3, n B u 4 N B r , 0 ° C HOH/CH2C1 2 , 2h 2 . CF3COOH, CH2C12 3. K2C03/aq.
Pfister, J.R. n
U
II
CH3CHCC1
t
c1
* ; Wymann,
91 %
MeOH Synthesis, (19831, 38
W.E.
1. Pip,
PhH, NEt3
O'C,
2h
2. LiA1H4,
Et20
87 %
20h
reflux, Suzuki, K.: Okano, K . ;
*
6h
Nakai, K.: Terao, Y.: Sekiya, M . Synthesis, (19831, 723
*
SECTION 93: Amines and Thiols - frau Alcohols --
nBuOH
0 II 1 . ( E t 0 ) 2 P N H C 0 2 t B u , DEAD PPh3, 0 - 2 5 " C , 2h
2. HCl/PhH,
RT,
h u s a r s k a , E.; Zwierzak,
12h
* A.
*
+
nBuNH3 C1
-
85% Liebigs -Ann Chem, (1986), 402
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
114
SECTION 94
SEXTION --94: Aminea fran Aldehydes
'&
/ N TMS
OMe
Hart, D . J .
*
1.
CH2=CHCH2MgBr THF/RT,
2.
30 m i n
HOH
QMe
; Kanai , K . ; Thomas, D . G . ;
--J Org Chem,
BH3*Py, PhCHO
PhNH2,
*
Yang, T.-K.
( 1 983) ,
48,
97%
289
CH2C12 AcOH,
RT
t
PhCH2NHPh
2h
P e l t e r , A.: Rosser, R . M . ;
Mills, S.
JCS Perkin I, ( 1 9 8 4 ) , 71 7 ---
2 PhNH2, PhCHO EtOH,
Yamashita,
NaTeH
RT,
* M . : Kadokura,
93%
*
M.;
73%
Suemitsu, R .
---Bull Chem S ~ C
Jwj
1 . NH2S02NH2,
2 . MeLi, Et20
PhCHO
3 . HOH-Py
*
PhCH2NHPh
20h
( 1 984)
57,
3359
Ht
>
PhCHCH3
4 . NaOH
Davies, F.A. ; Giangiordano, M.A.; S t a r n e r , W.E. Tetrahedron Lett , ( 1986) ,
I
NH 2 95%
3,3957
AMINES FROM AMIDES
SECTION 96
115
Related Methods: Amines from Ketones (Section 102) SECTION 95: --Amines fran Alkyl, Methylenes, -and Aryls
90%
Barton, D . H . R . :
*
LeGreneur, S . ; Motherwell, W.B. Tetrahedron Lett, (19831, 24, 1601 0 1-1
-
1 . M e O C N = S = N - C 0 2 M e , 36h
2 . 2,3-sigmatropic shift 3 . L i A 1 H 4 , E t 2 0 , 4h ref1 ux
*
Kresze, G. ; Miinsterer, H.
q - P h
NH Me
43 7;
J Org Chem, (19831, 48, 3561 ---
SECTION 96: --Amines fran Amides
PhCH2CNH2
1 . P h I O , CH3CN/HOH H C 0 2 H , 1 5 h , RT 2 . H30t
>
PhCH2NH2
Radhakrishna, AJCS.; Rao, C.G.: Varma, R . K . : Singh, B.B.; Bhatnagar, S.P. Synthesis, (1983), 538
85%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
116
SECTION 96
0
II
PhI(OCCF3)2, RT T H F / H O H / A g ,O 4h
t
L
Loudon, G.M. Boutin, R.H.
* ; Radhakrishna,
90%
A.S.: Almond, M.R.;
Chan,
-J
( 1 984),
H
Blodgett, J.K.;
9, 4272
38%
Zezza, C.A.;
Smith, M.B.*;
0
Ross, B.A.;
-J Org C h ,
NaBrOz, HOH
II
CH3CH2CHzCNH2
NaOH, 70°C
34%
Arhin, A . ; Cronin, P.L.E.
(19841,
*
3,4397
CH3CH2CH2NHz 73%
30 m i n
Kajigaeshi,
* S. ; Nakagawa, 1,
0
11
CH3(CH ) CN
/Me 'OMe
--
T,z-c \ /
T.: F u j i s a k i , S.
Chem Lett, (1984), 713
H
cH
/' E t O H , HC1 2. NaBH4
3. H t
Basha, F.Z.; DeBernardis, J.F.
*
M 9B r
*
0
CH3(CH2)4
N H
62%
-
Tetrahedron Lett, ( 1984),
25, 5271
SECTION 97
117
A M I N E S FROM A M I N E S Li
,
Et20,
2. LiA1H4,
Et20
1.
3L/
-t
0
Hwang, Y.C.:
4
Smith, M.B.
0
0°C
20% NaOH
3.
*
Chu, M.; Fowler, F.W. -J Org Chem, (1985), 1 . Et30+BF4-,
82%
50,
3885
CH2C1
0" C 2.
CH3N02, : 2
CH2=CHPh,
31 % Heterocycles, (1985), 3,2229
* ; 3S.h r oL fi fA, l HH%.
THF,
2d
NH C 0 2 C H 2 C h = C H 2
PPh3,
CHC13,
THF
P ~ I ~ ( d b a )H C~ O, O H ,
Minami, I.: Ohashi, Y.;
30°C
-6
Shimizu, I.; T s u j i , J.
-
*
Tetrahedron L e t t , (19851,
quant.
26, 2449
Related Methods: P r o t e c t i o n of 4mines (Section 105A)
SMZTION 97: Amines f m Amines
----
0
2 PhCH2SiMe3,
Y+
TBAF,
0-
*
24"C,
Vorbruggen, H. ; Krolikiewicz, K .
THF
>
18h
Ph
70%
-
Tetrahedron Lett, (19831,
2, 889
11 8
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 97
0
0-
Webb, T.R.
5 5%
*
Tetrahedron Lett, (19851,
Chastanet, J.: Roussi, G .
*
26,
3191
J Org Chm, (19851,
50, 2910
1 . LDA
M e1 ‘0-
2. CH2=CHPh 71%
Chastanet, J.
; Roussi, G .
t
+
%Ph
(&:I=
1:0.8
%
Ph
0.3: 0.6)
Heterocycles, (1985) , 23, 653
n
0
N ‘’
Kapnang, H.
2 nPrMgBr
: Charles,
G.
*
80%
Tetrahedron Lett, (1983),
2, 1597
SECTION 97
AMINES FROH AMINES
1 . HCl/MeOH,
Et20
PhSCl , CH2C12
CH2CH =CH2
2.
C H PIH P h
3 . K2C03, N a I , C H 3 C N
I
119
> I
4. Ni(R), EtOH
Ph
51 % Ohsawa, T . ; Ihara, M . ;
Fukumoto, K . ; Kametani, T. J Org Chem, ( 1 9831, 48, 3644 ---
1 . HCO,Et,
0°C
-
reflux
L
Meyers,
4 . LDA, -100°C 5 . MeI, -100°C 6 . N H 2 N H 2 , AcOH * . I . ; Fuentes, L.M. J
0
Ph
-
hv
PIo4 MeOH
(99%ee S ) -A
105, 117
Chem Soc, (19831,
*
TMS
Lan, A . J . Y . ;
40%
Q u i l l e n , S.L.: Heuckeroth, R 0 . : Mariano. P.S. JAmChemSoc, 984), 6439 ---Yoon, U.C.; Q u i l l e n , S.L.; Mariano, P.S. Swanson, R . ; Stavinoha, J . L . ; Bay, E. J A m C h e m S o c , ( 9831, 105, 1204 ----
5
106,
*
120
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 97
opC O O H NaBH4, THF 12h
OMe OMe
Ymada, K . ;
Takeda, M . ;
Iwakuma, T.
*
68% (60% ee)
JCS Perkin I, (1983), 265
5 % [PdCl 2 - C u C 1 2-NaC1 CH2=CH(CH2),NH2
Pugin, B. ; Venanzi,
6.5h
* 2 Am L.M. Ti02,
-
*
HCl] 60"C,
Me Me0
7 5%
Chem Soc, (1983),
P t , HOH
105,6877
*
R T , hv
H
*
Nishirnoto, S.; Ohtani, B.; Yoshikawa, T.: Kagiya, T. J Am Chem Soc, (19831, 105, 7180 ----
1 . n C H Br, C H C 1 3 , - 3 7
60°C
-
c
I
Me
2 . NaSPh, 2 - b u t a n o n e CH3CN,
I
r e f l u x , 24h
_?.C3H7 7 0%
Manoharan, T.S. ; Madyastha, K.M.*; Singh, B.B. ; Bhatnagar, S.P.; Weiss, U . Synthesis, ( 1983) , 809 Ind J Chem B, (1984), 23, 5 ----
SECTION 97
121
AMINES FROM AMINES
0 Y
0
LBuOK
1. x - B u L i , O"C,
lh
I
2 . nC8H17Br, 1 6 h
Me
-
-78°C
RT
*
Ahlbrecht, H. ; Dollinger, H. Tetrahedron Lett, (1984), 1 . BF3/THF,2 0 2 4 h , RT
70%
25, 1353
0
2 . NaOH/HOH 93%
Mora;es, H.R.*; Pdrez-Juirez, M.: Cueha, L.; Mendoza, L.: Fernandez, H.; Contreras, R . @ Ccamun, (1984), 2, 1213
9 Me
0 II
1 . C1COCHCH3 , D C E I c1 0°C
-
reflux
2 . MeOH, 5 0 ° C
-
*
-9
NH* HCI
reflux
97%
Olofson, R.A. ; Martz, J.T.; Senet, J.-P.*; Piteau, M.: Malfroot , T. --J Org Chem, (1984), 9, 2081
n
HO
NH
Bn
Sammes, P.G.
1 . A g B F 4 , MeOH
2 . HBF4/THF
* ; Smith,
t
Bn 51 %
S.
--JCS Perkin I, (1984), 2415
122
SECTION 97
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. tBuLi, 2.
THF,
-25°C
HMPA, C B u B r
*
I “\t - 1 3 ~
Meyers, A.I.
3.
NH2NH2
* : Edwards,
Meyers, A . I . * ;
Bn
N / \
Me/ ‘0-
Tokitoh, N . ;
W.F.; z,
Rieker,
I
*
1. tBuSiMe20Tf, MeLi,
THF
3 . BnC1,
10h
4.
THF
TBAF,
Okazaki,
Tokitoh, N.:
CH2C1
*
I,) I
Bn
58%
* R. ; Suzuki,
He*;Manabe, H. Chem Lett, (1984), 1937
--
2. MeLi, 3.
74%
H.: Maruoka, K . ; Yamamoto, H. Tetrahedron Lett, (1984), 25, 2367
1. tBuSiMe20Tf,
Me/ ‘0-
Bn
10h
O’C,
2.
B a i l e y , T.R.
t
C H 2‘C 1
OC02Et
0
u
JAm Chem (1984), 106,3270 P.D. : m e y , T.R.: Jagdmann Jr., G . E . --J Org Chem, ( 1 9851, 50, 1019
4 Me3A1
F u j i w a r a , J . ; Sano,
B
53%
P.D.:
Edwards,
?
H-
0
PhMgBr
Okazaki, R.
*
THF
CH2C1 t
I
Bn 74%
Tetrahedron L e t t , (1984),
25, 4677
SECTION 97
123
A E I N E S F R O M AMINES
RT
1 . FeC12, H O H , 2h
/ 'B n
H
2 . E D A , PlaOH, P e t e t h e r
-0
67%
Synthesis, (19851, 770
Monkovic, I . ; Wong, H . ; Bachand, C . 1 . NCS,
2OoC
0 . 1 Torr )c 2 . H02C(CH2)4C02H
C H CH CH N H
20° C, 0 . 1 T o r r
Guillemin, J . C . ;
Denis, J.M.
r-7 Y
B F3 2.
Me
E i s , M.J.
aq.
: Ganem,
B.
Synthesis, (19851, 1131
* O Et 2
t
94%
Tetrahedron Lett, (19851,
NaHTe
Barton, D.H.R.
nBuCH2CH2NHMe
t
NH~OH
E t O H , RT
Ph
85%
THF
1 . "Bu,CuLi, L
t
H C H ~ C H ~ C H ~ N ( c1
*
26,
W N H Ph
pH 6 - 7 t
1153
quant,
; Fekih, A . : Lusinchi, X . Tetrahedron E,( 1 9851,
2, 3693
124
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 97
-
e , graphite e l ec t r o d e
H
2.5h,
LiBr
20% a q .
Elof son, R.M. ; Gadallah, F.F.
: Laidler,
Can J ---
J.K. Chem, (19851,
[#L 1 . TiC13,
-78OC
Hb
71%
CH3CN
a\
63, 1170
THF
-
RT
~
2 . a q . NaOH
Murahashi,
* S. ; Kodera,
Y.
83%
Tetrahedron
E ,(19851, 26,
4633
1 . LDA, chexane - 7 8 O C
-
RT,
18h
H
2 . HOH
Pearson, W.H.
* ; Waters,
6' OEt
*
Haga, K . ; Iwaya, K.: Haga, K .
*;
63%
M.A. ; Oswell, K.D.
J Am Chem ---O#O,
Soc, (1986),
12h
c a t . pTsOH, r e f 1ux
PhCH3
-Ph iiiti
(1)
.
Ph ( 5 1 )
108,2769
-0 y Ph,
0 Et
90%
Kaneko, R. Bull Chem Soc Oohashi, M . ; Kaneko, R. B u l l Chem Soc
---*,(19861, 59, 803 ---*,(1984), 57, 1586
125
A M I N E S FROM HALIDES
SECTION 100
Review: "Nucleophil i c Additions t o Tet rahydropyridinium S a l t s : Applications t o A 1 k a l o i d Syntheses"
Stevens, R.V.
*
Accts Chem Res, (1984),
17, 289
SECTION 98: Amines frau Esters Pip H O C H C H = C H C H OAc
THF,
(El Gene^, J . P .
20°C
H O C H C H = C H C H 2-h
(L)
cat. P ~ ( P P ~ ~ ) ~
* ; Balabane,
lh
3 6 5%
BBckvall, J.E.*: Nystrijm, J.E. Tetrahedron @, ( 1 9831, 2, 2745
M.;
CH 2=CHCH 2 0 A ~ Pd(PPh3)4
NEt3, T H F , 2 5 O C
H B e r g b r e i t e r , D.E.
* ; Chen,
----
B.
84%
JCS Chem Carm, (1983), 1238
SECTION 99: Amines fran Ethers, Epoxides,
and Thioethers
No Additional Examples
Nishiyama, K.*:
Tanaka, N.
JCS Chem Ccnm, (1983), 1322
126 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
6
1 . Mg, THF
50%
*
Takahashi, T.:
Sekiya, M. JCS Chem Cam, (19841, 794
---
1 . M g , Et,OL
Br I
0
2. (Ph0)2P-N3 #'
-
Et20, -72°C 3. HOH Mori, S.;
6"'
t
2.[Me3Si12NCH20Me 3. MeOH
Morimoto, T.;
SECTION 100
Aoyama, T.; S h i o i r i , T.
*
+
RT
89%
-
Tetrahedron Lett, (19841,
gR
25, 429
ref1 u x
H
R R
Me
8 = LBu ( 92 *9 5 % Tetrahedron E,(1983), Hrubiec, R.T.; Smith, M.B. =
(
91 %
HMPA, 15OOC
*
24h
.
Y
GUDtOn. J.T. J U ~ .C, .D ;
* J . P . : Baker,
: Idoux, Rampi, R.c.
92 ) 8 ) 2,5031
76% C.;
-J Org Chem,
Colon, C.:
(19831,
48,
Crews, A.D.; 2933
AMINES F R O M H A L I D E S
SECTION 100 Br
-n B u 3 S n N E t 2 ,
NEt,
PhCH3
*
PdCl 2 ( g T o l 3P)2 100°C, Kosugi, M.;
Kameyama, M.;
3h
61 %
M i g i t a , T.
PhBr,
*
Chem Lett, (1983), 927
10% Pd(PPh3I4
3 KOH, cBu4NBr
QBEt2
THF,
*
reflux, Ih
I s h i kura, M. ; Kamada, M. ; Termhima, M.
85%
*
Heterocycles, ( 1 984),
22,
265
EN..
,C’
1 . Me3SiCH2NMe2
Nakano, M . ;
127
acetone t 2 . C s F (KI), H M P A R T ; 206 7 4% Sato, Y. JCS Chem C m , (1985), 1684
*
---
Me0
PhCH3, l h
7 6% Malmberg, H . ; N i ls s on, M.
Review:
*
Tetrahedron, (1986),
2, 3981
Y opper A s s i s t e d Nucleophilic S u b s t i t u t i o n of Aryl Halogen”
Lin dl ey, J.
*
Tetrahedron, (19841,
40,
1433
128 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 102
SECl'ION 101 : Amines fran Hydrides
--
1. nBuLi, 2.
TsN3,
Et20,
3. i c e 4.
RT,
Et20,
KOH/Ni(Al),
24h
0°C
0
-
25°C 80%
Narasirnhan, N.S.; Ammanamanchi, R.
Tetrahedron L e t t , (1983), 24, 4733
Q"
CN
NH3,
hv,
a q . CH3CN
88%
*
z,
Yasuda, M . ; Yamashita, T.: Matsumoto, T.; Shima, K.: Pac, C . --J Org Chem, ( 1 9851, 3667
b
SECTION --102: Amines fran Ketones N-0 Ms
1. Me3SiOTf 2.
Sakane, S.; Maruoka, K . :
*
Dibal-H
Yamamoto, H.
*
*
3
Tetrahedron L e t t , (19831,
87%
24, 943
129
A M I N E S FROM KETONES
SECTION 102
5 Dibal-H CCH3(CH2)4]2C=NOH
0-20°C
*
[ C H 3 (CH2 I 4 l 2 N H
85%
*
Sasatani, S.; Miyazaki, T.: Maruoka, K . ; Yamamoto, H. Tetrahedron Lett, (19831, 24, 4711
L
II
CH3 ( C H 2
N O M ~
-
1 . Et2A1C1 i+
2.
Dibal-H
CH3(CH2I1
0 H
53%
Sakane, S . ; Matspura, Y.; Yamamura, Y.; Ishida, Y.: Muruoka, K . ; Yamamoto, H. J Am Chem Soc, (1983), 105, 672 ----
& :
Ac OH
nBu3P
v
OAC
N
'OH
6
Barton, D.H.R.:
0
A b e , K.;
C7H15
'Y H NHz
NaBH3CN
PhSSPh TH F
94%
'Y'
Ac OH
CN NHz 'good y i e l d '
Na CN
Motherwell, W.B.; Simon, E.S.; Zard, S.Z. --JCS Chem Cam, (1984), 337 1 . NaBH3CN,
NaBr
MeOH,
4d
2 . pH 3 , 3.
RT,
RT, 3h
+
HO Me
pH 1 1
Okmura, H.: Tsugoshi, T.; Nakamura, N. Synthesis, (19841, 597
H 80%
*
H C 7 H 15
130 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
N N Me,
1 . E B u L i , THF,
-78OC
2.
-78°C
P h S C u , THF,
SECTION 102
0 II
3. CH2=CHCCH3, 4. H30
* ; Liu,
Kelly, T.R.
t
82%
_--J Am
H.
Chan Soc, (1985),
1 . NaN3,
y 3
-70°C
55OC,
BrCH2CH2CHCCH3
107, 4998
DMSO
18h
I1
0 Vadtier,
M.:
* 65% RT, 1 2 h Lambert, P.H.: Carri;, R. Bull Chem Soc Fr, (1986), I1083 ----
H*r.F H 3
p""" \
1 . LiA1H4,
THF
NHZ
t
2. HOH
HIlkPh Me 73%
(44% ee R )
I t s u n o , S.*: NBn
Me,
Me'l
II
C-C-CH3
CH2C1 Sulmon, P.:
Tanaka, K . ; 1.
Ito, K.
-Chem Lett,
2 L B u O K , THF reflux,
2 . H30
De K i m p e , N .
2h
t
* : Schamp,
* N.
JCS Chem Carm, ---
(1986), 1133
JNH I
(1986), 1677
Related Methods: Amines from Aldehydes (Section 94)
95%
SECTION 103
AMINES F R O M NITRILES
131
SECTION 103: Amines Prom Nitriles
--
1 . 3 LiA1H4, T H F reflux, 15 min CN
New,
CN
2 . H30
* J.S. ; Yevich,
t
NH,
62% Synthesis, (19831, 388
J.P.
1 . Dibal-H, -70°C
-
PhCH3 RT
>
2 . NaF, O ’ C , 3 0 m i n I 85% 3 . H O H , 0°C - RT * Overman, L.E. : B u r k , R.M. Tetrahedron Lett, (1984), 25, 5737 HSiMej,
CO
2
b
c a t . Co2 ( C O ) 8 P h C H 3 , - 2 0 - -60°C
,Ivi) 61 %
Murai, T.*; Sakane, T.; Kato, S. Tetrahedron Lett, (19851, 26, 5145
6
Weiberth, F.J.:
-
1 . iPrMgC1, T H F
r e f l u x , 2h 2. LiNH2,
PhC02Na
*
“5 60%
Hall, S.S.
)c
J Org Chem, (19861, ---
2,5338
132 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION
SECTION 105
104: Amines fran Olefins
aq. NaHC03, 10°C 3 . 10% H C 1 4. 3 N N a O H Kabalka, G.W.
* ; McCollm,
-J Org Chem, C.W.:
60%
Kunda, S.A.
(19841,
2, 1656
Review: "Amination of Alkenes" Casc,
M.B.; Lattes, A.:
Perie, J.J.
Tetrahedron, ( 1 9831,
2,703
SECTION --105: Amines from Miscellaneous Compounds 1. nBuLi
CH3Li.NHMeOMe Kokko, B.J.;
Beak,
* P.
t
2. H O H
CH N HnBu 72%
Tetrahedron
G,(19831, 24, 561
1 . ( o t 3 C H , 1 1 O°C 4h
&02
Lloyd, D.H.:
2. T i C 1 3 Nichols, D . E .
H
*
62% Tetrahedron Lett, (19831,
2, 4561
AMINES F R O M M I S C .
SECTION 105
Ph
1 . L D A , THF,
Nco
-nC3 H7 B r ,
''',Po
-
3.
-78OC 3h
*
EtOH,
2 . NaBH4, 80°C,
133
35h
70% H2S04,
18h
H
""0 94%
(98% ee)
* (1983), 9, 7754
Guerrier, L.: Royer, J.; Grierson, D.S.: iiusson, H.-P.
_--J Am
1 . SnC12,
CN
CI
Bellamy,
~
Vaultier, M.; R z l l C g H 13
Soc,
2HOH,
EtOH
7OoC, 3 0 m i n 2.
* F.D. ; Ou,
0-
C-
5% a q .
*
NaHC03
1 . P P h 3 , THF, 2. HOH, 12h
Knouzi, N.:
*
95%
1 2 h )-.
Carrie, R.
Tetrahedron
4 HC02NH4, Pd/C,
NaTeH,
*
96%
Tetrahedron Lett, (1984), 25, 839
K.
E ,( 19831, 24, 763 MeOH
-+
Gartiser, T.; Selve, C . ; Delpeuch, J.-J. R = Bn
CI
CN
Tetrahedron L e t t , ( 1 9831,
EtOH/Et,O,
Suzuki, H. ; Takaoka, K .
RT
Chem L e t t , (19841, 1733
93%
24, 81 %
1609
134 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . BC13,
PhH
*
10 m i n
2. H30
Zanirato, P.
*
t
H
JCS Chem Cam, -,-
1. tBuLi,
2.
(1983), 1065
THF,
-78°C
-
RT,
3h
?Q
3 . 3 N: lH 2: N2 H 29 ,5 % pEHt O 8H,: A c1 O5 Hh :
L N. '
91%
I(CH2)4C1 -78OC
.Me
S E C T I O N 105
OMe
61%
t -Bu
Meyers, A.I.
* : Marra,
26, 5863
Tetrahedron E,(1985),
J.M.
t
Me2N=CH2 C 1 PhSnMe3
CH2C12,
24h
w
PhCH2NMe2
r e f 1 ux
Cooper, M.S.: N02
I
Heaney,
,
OH
CH 3 C C H 2 C H 2 C H C H
I
* H.
1 . NiC12.6H20 N a B H 4 , MeOH 2.
CH3
Osby, J.O.
: Ganem,
Tetrahedron E,(1986),
* B.
Dowex-50(Ht) NH3/MeOH
65%
3, 5011
,
NH2
*
OH
I
CH 3CCH CH CH CH
I
CH3
-
Tetrahedron Lett, (19851,
7 6%
26,
6413
SECTION 105
R-
AMINES FROM M I S C .
9-
NapTe/aq.
*
Suzuki, H. ; Manabe, H.:
R-
Ph
NaOH/dioxane/50°C
Inouye, M.
1.
iBu2Te
2.
TiC14/CH2C12
:
~
O
H
Boldrini , G . P .
R-
Chem Lett, (1985), 1671
3 . HOH
Me3Bn,
R
2. aq.
*
74%
-
HFe(C0)4-
HC1
3.
Na2C03
; Cainelli , G . ; Urnani-Ronchi,
-J Organomet Chem,
Q
95%
t
Chem Lett, (19861, 549
H a n a z a k i , Y.
Suzuki, H.*;
135
80%
* A.
(1983)
2113,
1 . [ H g C l ? / T H F / M g , RT] t 2 . T i C 1 4 , L B u O H , 0°C HO * Syn Coaarm, (1983), George, J.; Chandrasekaran, S.
R = -CH2CH2CHMe2
HC03NH4, MeOH,
Ram, S.:
Ehrenkaufer, R.E.* EtOH/HOH, ASO, Y.;
Watanabe, Y .
-
40 m i n
*
Tetrahedron=, 80°C
PhH
94%
13,495 82%
(19841,
3, 3415
-+
72%
*
O t s u b o , T.: Ogura, F. Chem Lett, (1984), 853
Rz O O M e
R = QNO2
RT,
[PhTeTePh/NaBH4],
Rz Ph
Ohira, N.:
1 O%Pd/C
195
* : Ohta,
--
RuC12(PPh3)3,
NEt
T.;
HCOOH
*
, E t OH,i%?CTv5F--T s u j i , Y.;
97%
Hiyoshi, T.; T s u j i , Y .
Bull Chem Soc s,(19841, 57, 2440 --P t C 1 2 ( P P h 3 ) 2 , SnC14 NEt3, a q . d i o x a n e , CO * quant.
RT Watanabe, Y .*: T s u j i , Y.; O h s u m i , T.; Takeuchi, R. Bull Chem Soc (19841,
--- s,
57, 2867
136 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 105A
600 p s i H2,
@=
polystyrene Baralt, E.; Holy, N.
SECI'ION
=:
EtOAc,
* --J Org Chem,
100°C
(19841,
80%
2, 2626
Protection of Amines
Related Methods: Amides from Amines (Section 82) Amines from Amides (Section 96) /NH-BoC 1.
Kim,
NEt3
9
*
iP r C H
\
COOH
2. Ht
0
* S. ; Chang,
i P r C H , ,NH 2 COOH
H.
--JCS Chem Carm, (19831,
98%
1357
c1 I
BOC-OCHCC13,
PhCH2NH2
20"C,
Barcelo, G.;
H
Kim,
* S. ; Lee,
+
PhCH2NHBOC
s a t d . K2C03
S ene t, J.-P.;
0
THF
Sennyey,
* G.
-J Org Chem,
O S B O C CH2C12,
RT, 1 5 m i n
J.I.; Y i , K.Y.
91 %
50,
*o
( 1 9851,
3951
0 t - Bu 95%
--will Chem Soc s,(19851, 58,
3570
SECTION 105A
Kapnang, H.; Charles, G .
6
137
PROTECTION OF AMINES
Ph3CSC1,
*
Tetrahedron
aq.
THF,
E, (1983), 24,
Na2C03
--+
3233
NHSC Ph,
96%
1 . T M S - I , CH,Cl,, L +--- . 2. aq. EtOH
Branchaud, B.P.
*
Me2Si\
L
-78°C
-.-
-.-
_-
TRS g r o u p
J Org Chem, (1983),
,CH LI
La
IY I'I
CH -
e
1'1
-
e
g, 3538
Zn12
2'S,iMe2,
I*
(trityl sulfenyl)
92%
/ /
LI
IY
140°C
si
\..'Si
\
9 2 7
2 MeOH,
Guggenheim, T.L.
PhCH2NH2
*
c a t . pTsOH quant.
-
Tetrahedron Lett, ( 1 984),
( T M S ) 2~~~
3, 1253 0
*
PhCH2NHCOCH =CH2
C1 F,0CH=CH2
Raucher,
0 * S. ; Jones,
D.S.
II
97%
Syn Cornnun, (19851,
3,1025
138 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 105A
1 . BOC20, 2. PhCH2CH2NHAc
MeCN
Et2NCH2CH2NH2 MeOH,
3.
DMAP,
PhCH2CH2NHBOC
94%
l h
NH2NH2/MeOH,
Grehn, L.; Cunnarsson, K.:
t
3d
Ragnarsson, U .
JCS Chem Cam, (1985), 1317 ---
nii
1 . PhCH=CHCH20COR HOH, N E t 3 , DMF
y 3 NH2CHCOOH
HOOCCH2,
t
NH I
c=o
2 . H,O+
I
I
P hCH =CHCH
Kinoshita, H.*; Inomata, K.: Kameda, T.: Kotake, H. Chem L e t t , (19851, 515
/"
9 5%
--
P~CH~CH~NHCBZ CH2C12,
King, P.F.
* ; Stroud,
Overman,
Tetrahedron
S.G.
,
NEt3,
MeCN
<
PhCH2CH2NH2
80% a q . AcOH, 30 rnin
* L.E. ; O k a z a k i ,
E ,(19851, 26,
1415
>
92%
RT
U
+
83%
PhSitBuCl
1" only
2h
RT,
U
25°C
7 4%
M.E.; Mishra, P. Tetrahedron Lett, (1986), 27, 4391
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 8 PREPARATION OF ESTERS
--
SECTION 106: Esters from Acetylenes
nB u C=C C H
P d C 1 2 , C u C 1 2 , HC1 O2
1 a t m C O Y MeOH R T , 2h
nB u
*
H
* Alper, H. ; Despeyroux, B.;
Woell, J.B. Tetrahedron Lett, (19831,
1.
nBuC=C- I
1-J+h2~~
Hoshi, M.; Masuda, Y.: Arase, A.
/
‘c = c \
C02Me
72%
3, 5691 0
2. Z B u S M g B r , -50°C
HMPT 3. H 2 0 2 , N a O H
/CH 3
- \
*
*
I1 nB uCH CS n B u 83%
JCS Chem C a m , (1985), 714
SECTION 107: --Esters from Acid Derivatives
The following types of reactions are found in this section: 1. Esters from the reaction of Alcohols with Carboxylic acids,
Acid Halides, and Anhydrides.
2. Lactones from Hydroxy Acids.
3. Esters from Carboxylic Acids and Halides, Sulfoxides, and Miscellaneous compounds.
140 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION
0::: 0
br
1. 2 PhP(TMS)2 CH3CN, 4 h , -15°C
C02Me
2. 4 MeOH,
C02Me
24h ref1 u x
62%
*
Appel, R . ; Htlnerbein, J.: Knoch, F. Angew Chem Int Ed Eslgl,
(19831,22, 61
0
0
I1
ClCOBn, NEt3, 0°C C H ~ ( C H ~ ) ~ C O O H c a t . DMAP, C H 2 C 1 2 Kim,
* S. ; Lee,
30 m i n
97%
J . I . : K i m , Y.C. J Org Chem, (1985), 50, 560
-
1. nBu3SnStBu,
PhCH2SC1
RT,
* ; Aida,
@="1 Amos, R . A .
P h C H SS t B u
90%
Tetrahedron Lett, (1 9831, 2,51 73
-
@P P h 2 0 C H 2 0 H
(f)
0
II
Et20
T.; Chan, T.H.
PhCH=CHCOOH
24, 3365
CHC13
3 min
2 . a q . KF, Harpp, D.N.
II
CH3(CH2)6COBn
Tetrahedron Lett, (l%3),
011
107
THF, DEAD,
25°C
PhCH=CHC02Bn
(L)
86%
ystyryl
; Emblidge, R.W.: Havens, N . --J Org Chem, (1983), 48, 3598
SECTION 107
ESTERS FROM A C I D S
c,',"O
e - x y l ene,
Mukaiyama, T.
* : Ichikawa, J.:
r e f 1ux
* Widmer, U.
HN- CH 2CH P h
86%
Asami, M.
(tBuO)2CHNMe2, PhCH3,
Go
.*
PhCH2CH2NH2, 3 h
H
141
Chem Lett, (19831, 683
80°C
30 m i n
* 82%
Synthesis, ( 1 983 1 , 1 35 nPrOH,
PhCOOH
RT
Py,
30 m i n
N '
*
*
PhCOCH2CH2CH3
o z N O N O ~ CI
94%
Takimoto, S. ; Abe, N.; Kodera, 'Y.; Ohta, H. Bull Chem Soc (19831,
A%
Ph
kOOH
--- s,
cone. H 2 S 0 4 20"C,
72h
*
56,
639
Ph
84% Sychkova, L.D.; Kharitonova, O.V.; Shabarov, Yu.S. J Org Chem USSR, (19831,
2, 1298
142 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Mandal,
* A.K.
lh ---Ind J Chem B, (1983), 22, 505
H? CHCH2CH=CH(CH2)7COOH I
llCgH1 3
(L)
Cais, H.-J.
*
SECTION 107
88%
1 . Me2NCrCC02Me 2 . CH2C12, 40°C
*&o
cat. camphor sulfonic acid
0 82%
Tetrahedron Lett, (19841, 25, 273
/-w < c 0
T M S O ( CH2), 4 C 0 2 T M S
nPr2BOTf PhCH3, ref1 ux 8h
>
(
* K. : Kotake,
Taniguchi, N.; Kinoshita, H.: Inmata, Chem Lett, (19841, 1347
--
CH~(CH~)~COOH
*
Kim, S. ; Lee, J.I.:
BnOH, CH2C12 RT, 2h KO, Y.K.
0
*
H.
94%
CH3(CH2)6C02Bn 94%
Tetrahedron Lett, (1984), 25, 4943
ESTERS F R O H ALCOHOLS
SECTION 108
e CH3CH2CH2COOH
-,
EtI,
143
P t electrodes
Et4NOTs, RT
CH3CH2CH2C02Et
DMF
96%
*
Nonaka, T. : Fuchigami, T. -Chem Lett, (1985), 371
Awata, T.; Baizer, M.M.;
Further examples of the reaction RCOOH + ROH + RCOOR are included i n Section 108 (Esters from Alcohols and Phenols) and Section 10A (Protection of Carboxylic Acids). SECTION 108: Esters from Alcohols -and Thiols
- --
0
b
II
0
OCPh
II
&H
3 PhCOTf,
CH2C12
py,
- RT
-78°C
81%
Brown, L.: Koreeda, M.
is.
*
--Ja C h e m i i i ,
8 Br2
5 Ni(OBz)2
OH
20°C
*
Doyle, M.P. ; DOW, R.L.:
9,3875 (1983), 1113
J Org Chem, (19841,
>
d-
0
0
+
99%
Bagheri, V.: Patrie, W.J. J Org Chem, (1 983), 48, 476
144 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 108
84%
* Kageyama, T. ; Kawahara, S.; Kitamura, K.: Chem Lett, --
Ueno, Y.; Okawara, M. (1983), 1097
NaBr03-HBr
*
HO(CH2)40H CC14,
5h,
37°C
78%
*
Kajigaeshi, S. ; Nakagawa, T.; Nazasaki, N.; Yamasaki, H.: Fujisaki, S. Bull Chem Soc Jpn, (1986), 2,747 ----
f o H
RhH( P P h 3 I 4
\
? OH
PhH,
50"C,
10h
t
t 82%
*
*
Ishii, Y.; Suzuki, K.; Ikariya, T.; Saburi, M. ; Yoshikawa, S. J Org Chem, (19861, 5l* 2822 * Ishii, Y.; Osakada, K.; IEariya, T.; Saburi, M. : Yoshikawa, S. -J Org Chem, (1986), 2,2034
,
CH20H
(CH2)8 CH20H
'
(bipy)H2CrOC1
N O
C'
>
\
/
CH2C12, R T
*
Chakraborty, T .K.; Bhushan, V.; Chandrasekaran S . Ind J Chem B, (1983), 22, 9 ----
2
0
ESTERS F R O M A L C O H O L S
SECTION 108
0
t
I1
0
1 . Me2N=CHOCPh, E t 2 0 2 0 ° C , overnight
CH3CH2CHCH20H
145
II
+
CH CH C H C H 2 0 C H
*I
2 . d i l . a q . H2S04
* Barluenga, J. ; Camps,
CH3 65%
P.J.; Gonzalez-NGez, C.; Asensio, G. Synthesis, ( 1 985) , 426
CO, THF, C H 2 = C H C H 2 C H 20H
C u C l 2,
22
PdC12
HC1
RT
*
0
overnight
6”
*
Alper, H. ; Leonard, D.
JCS Chem Comn, (1985), 511
+(i C02E t
C O Y C O ~ ( C O ) ~E , t O H 900 p s i , 1 9 0 ° C HOH, 24h
CI
(jH
60%
* Shim, S.C.; Antebi, S.; Alper, H.
CI
68%
6
--J Org Chem, (19851, 9, 147 0
5cch3 II
0 I1
CH3CSH,
Zn12
CH2C12,
30 m i n
\
0 Me
?4
Gauthier, J.Y. ; Bourdon, F.: Young, R.N. Tetrahedron E ,(1986), 3, 15
85%
146 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
HLADH = H o r s e L i v e r A l c o h o l
Lok, K.P.;
Dehydrogenase
* Jakovac, I.J.: Jones, J.B. J Am Chem Soc, ----
SECTION 109
(97% ee)
(19851,107,2521
Further examples of the reaction ROH + R'COOR are included in Section 107 (Esters from Carboxylic Acids and Acid Halides) and Section 45A (Protection of Alcohols and Phenols). SECTION 109: -Esters from Aldehydes LiW02,
2 0 PhCHO
75"C,
0
THF
II
t
72h
PhCOBn 89%
* J.S.
Villacorta, G.M.; Filippo Jr., --J Org Chem, (19831,118, 1151
Me \Nx
'j
N
M<
i
Me
1. nBuLi, 2.
THF,
(NEt2)3TiC1,
-78°C THF,
3 . c C ~ H , ~ C H O , THF,
-20°C t reflux
5
Ph
4 . MeOH, H t 5. B F 3 * 0 E t 2 , mcpba
*
C C g H 17 9 6%
Roder, H.: Helmchen, G. ; Peters, E.-M.; Peters, K.; van Schnering, H.-G. Angew Chem Int Ed Engl, (19841,3 , 898 --__--
SECTION 110
iP r C H O
ESTERS
FROM ALDEHYDES
147
Li i 1 . PhS-C-OMe , THF, -78-25°C SiMe3 2 . Me3SiC1, N a I , MeCN 3. A1203
0
I1
I
i PrCH2CS Ph
t
@
86%
*
Hackett, S.; Livinghouse, T. Tetrahedron Lett, (1984),
Nakamura,
6
O"C, l h
* E. ; Oshino,
(61
* I.
H.; Kuwajima, J Am Chem Soc, (19861, ----
C H 3 C H = C H C 0 2 M e , Sm12 H M P A , 0°C. 1 m i n
Otsubo, K.; Inanaga,
25, 3539
* J. ; Yamaguchi,
*
95%
39)
108,3745
do 96%
(EJg
=
1 :1)
M. Tetrahedron E,( 1 9861,
3, 5763
Related Methods: Esters from Ketones (Section 117) SECTION 110: --Esters from Alkyl, Methylenes, and Aryls
No examples of the reaction RR + RCOOR' or R'COOR (R,R' = alkyl aryl, etc.) occur in the literature. For the reaction RH + RCOOR' or R'COOR see Section 116 (Esters from Hydrides).
148 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 111
OAc 1
P b ( O A c ) 4 , AcOH CH3(CH2)4CH3
t
sun1 i g h t
6d
Bestre, R.D.;
CH3CHCH2CH2CH2CH3
Cole, E.R.;
50%
+
CH CH C H C H 2 C H 2 C H 3
2l
* G.
OAc 45 % Crank, Tetrahedron Lett, (1983), 2, 3891
R u C l 2 * 3 H 2 0 , DMF NaI04, RT,
HOH,
CC14
16h 88%
Chakraborti, A.K.;
Ghatak, U .R.
Synthesis, (19831, 746
SECTION 1 1 1 : --Esters from Amides
0
II
CH 2=CHCNEt2
1.
P h S 0 2 N a , AcOH/HOH
2.
P4Sl0,
r e f 1ux NaHC03,
3 . M e 2 S 0 4 , MeCN,
4. K C N , 1 5 h
5 . nC3H71,K O H ,
6.
DME
*
12h aq.
PhS02CHCH2C02Me
THF
44%
t r i c a p r y l NH'C13N H C 1 , MeOH, 1 5 h
*
De Lombaert, S . : Ghosez, L. Tetrahedron --Lett, (19841,
25, 3475
SECTION 113
149
ESTERS FROM ESTERS
SECTION ---112: Esters f m Amines 1.
nBuNH2
\
S I1
>
nBuSCOEt
2 . KSCOEt II
* Elshafie, S.M.M. 1.
B n N H ,L
@I..'' S
A
70%
Org Prep Proc Int, (1983),9, 225 ---Ph
0
2. Ag(OAc)2
P h C H OAc
>
3 . 150°C
53%
* Molina, P. ; Alajarin, M.;
De Vega, M.J.P. Syn Cornnun, (1983), 13,501
SECTION 113: --Esters f m Esters
so+m'
Conjugate reductions and conjugate alkylations of unsaturated esters are found i n Section 74 ( A l k y l s from Olefins).
0
A O ; C H = C H Me
* Clive, D.L.J. ; Beaulieu, P.L.
\/a n
7n \
63%
JCS Chem C a m , (19831, 307
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
150
0
1. X,
* Ii
0
-8OOC
R OCCH2CH3 2 . B n B r , HMPT, -63OC X = LICA/THF/EHMPT
X
SECTION 113
= LICA/THF/HMPT
*
t
R OC-Ph
S:2R = 3 : 9 7 ) 8 9 % ( 234%
(25:2R =
Helmchen, G. ; Selim, A , ; Dorsch, D . ; T a u f e r , I.
Tetrahedron Lett, (1983),
1. LICA,
THF,
;
* II i
95:5)
24, 321 3
65°C
CF3S020S i E t TH F
2. H2, 3.
Pt,
CH2N2,
EtOH
*
Et20 84%
Brunner, R.K.; Borschberg, H . J .
Helv Chim Acta, ---
0
II tBuOH,
0 !I Hg(OCCF3)2
CH3CN,
25"C,
( 1 983),
66,
C02Me
2608
0
II
COtBu
4 5 rnin 90%
Chan, W.K.:
Masamune, S.*;
Spessard, G.O.
-Org Syn,
(19831,
61,48
ESTERS FROM,ESTERS
SECTION 113
151
4c3H7-
p
0 II
1. Hg(OCCF3)2,
25"C,
C02Me
CC14
12h
2 . nBu SnH, AIBN -TH?, 25oc 3. a q . K F
coiium, D.B.*; Mohamadi, F.: Hallock, J.S. ---J Am Chem Soc, ( 1 983),
c
AcO
C s O A c , DMF 105OC, 24h
t-BU
t-Bu
54%
* Huffman, J.W. ; Desai, R.C.
CH2=C
\
6882
-0
OMS
/
105,
CH2C3H7 86%
Syn Carmun, (19831,
2% Pd(OAc)2,
Ph CH20COEt II * 0
4% PPh3,
50°C
*
5h
/
Ph
\
CH2C02E
5 atm. CO
Tsuji, J . ; Sato, K.: Okumoto, H.
tBuOH,
CH2=C
13,553
J Org Chem, (1984),
CH3CN,
80%
9, 1341
RT
> CuBr2, 0.3h 89%
for t h e p r e p a r a t i o n o f h i n d e r e d esters
* Kim, S. : Lee, J.I.
-J Org Chem,
(19841,
9, 1712
SECTION 113
152 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
S
1 . L D A , THF, -78°C
C H C O Me 1 2 2 CH2Ph
2 . Me3SiC1, - 7 8
-
0°C
*
II
CH2COMe I CH2Ph
3 . H2S, 25°C
* Corey, E . J . ; Wright,
E,(19841, 25, 2639
C H 2 = C H n B u , AIBN
0
il
CH3CHCOSnnBu3 I I Kraus, G.A.
Tetrahedron
S.W.
7 5%
P h H , r e f l u x , 8h
* ; Landgrebe,
n-Bu 7 5%
C02Me
1 . KBH4,
PGrim, E.L.:
2 . HS R e i s s i g , H.-U.
MeOH, RT 16h
*
*
9 5%
J Org Chem, (19851,
Cg2Et
1 . 2 . 2 LiCHBr2, T H F -90°C, 1 0 m i n LTMP 2 . 6 E B u L i , - 9 0 - 3°C 3 . H + / E t O H , 0°C
*
25, 3939
P
Tetrahedron Lett, (19841,
K.
50,
242
-6
Kowalski, C . J . ; Haque, M.S.; F i e l d s , K.W. J Am Chem Soc, (1985), ----
C02E t
72%
107,1429
SECTION 113
153
ESTERS FRON ESTERS
[l, 5 - H D R h C 1 1 2 , PhCH 2 B r
HC02Me,
RT
*
K I
PhCH2C02Me
1 0 0 psi CO
quant.
*
Buchan, C . ; Hamel, N . ; Woell, J . B . ; Alper, H. JCS Chem C a m , (1986), 167
---
0
A 8
1 , Ce, c a t . 1 2 , , T H F
CH-Br
I L
2 . PhkCH3,
CH2C02Me
RT,
,>
2h
Ph Mt
0
7 0%
*
Fukuzawa, S. ; Fujinami, T.; Sakai, S. JCS Chem Conm, (1986), 475 --C H,OAc
OAC
0
60°C
II
0
)M
AcO
2 3
quant.
Patt, H.: Wichelhaus, J . Nouv J Chem, (1986), ---
Wulff, G.;
10,143
Review: "Sulfur Mediated Ring Expansions i n T o t a l Syn t h e s i s" Vedejs, E.
*
Accts Chem Res, (19841,
6'
CH2CH 1 2
3, 358
154 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 114
SECTION 114: --Esters from Ethers, Epoxides, p J Thioethers e
Me3SiC1, A c 2 0 , 2 4 ° C
Sarma, J . C . : R.P."
Barbaruah, M . ;
Barua, N.C.:
Sharma, R.P.':
I
A
c a t . conc. H2S04
A
P I bI
CI
Barua, N.C.:
Sarma, D.N.;
Sharma,
etrahedron, ( 1 9861, 42, 3999 Baruah, J . N . Tetrahedron Lett, (1983), 24, 1189
\
,c=c=o
Zn(activated)
1
A
7 6% Marherbe, R.;
Moody, C . J .
t
Rist, G.; B e l l u z , D . J Org Chem, (1983), 48, 860 ---
JCS Chem Comn, (1983), ---
1129
70%
4 0 a t m . C O , KI
1 8 - c r o w n - 6 , 120°C 4h R o k i c k i , G . : Kuran, W.
t
: Pogorzelska-Marciniak, Monatsh Chem, ( 1 9831,
68 % B. c, 205
71 %
SECTION 115
Bonadies,
E S T E R S F R O M HALIDES
* F. : DiFabio,
Uguen, D.
SETION
R.: -J Org Chem, (19841, 1491, 2647
Tetrahedron E ,(1984),
115: Esters fmm Halides
Me2 C = C H C H 20Ac
45%
8 5 - 9 0 ° C , 10h
*
7 0%
* Bonini, C.
C u , CuOAc2 LiOAc, H O H r e f l u x 2AcOHIAc,O L
Me2C=CHCH2SPh
5,541
Sulfonates
* R-C02R'
R- X
R = B n , X = C l
R'
= Me
Sawicki, R.A.
*
.
CO/MeOH/MeOK/A1203
t
c o ( c o ) 4 - / c 0 2 ( co ) 8
J Org Chem, (1983),
48,
R = B n , X = Br R ' = iPr
57%
5382
R = B n , X = Br C O Y MeOH, K2C03 R ' = Me Fe(CO)5, R T * Tustin, G.C. ; Hembre, R.T. -J Org Chem, (1984),
Woell, J.B.;
155
68%
+,
3,7761
1 . T i ( O i P r ) 4 , C O , 75OC
*
c a t . [ l ,5-HDRhC1I2 2 . a q . NaOH * Fergusson, S.B.: Alper, H. -J Org Chem, (1985), 50, 2134
98%
156 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
>
(Et0)3B, COY K I c a t . [ l ,5-HDRhC1I2
R = B n , X = C l
R' = E t
SECTION 1 1 5
71 %
Alper, H.: Hamel, N.: Smith, D.J.H.; Woell, J.B. Tetrahedron Lett, (1985) , 26, 2273
R = Ph R ' = Me
X = Br
C O Y MeOH,
CH3C02Et
C O ( C O ) ~ - , NaOH,
Foi, M. ; Francalanci , F. ; Bencini , E. ; Gardano, A. J Organornet Chem, (19851, R'
NaOMe,
X = I
R = a-naphthyl,
CO,
HMPA
PhPdI(PPh3)2,
= Me
R'
->
*
c a t . [l ,5-HDRhC1I2, BuOBu, K I , 75°C
= Bn X = Br = nBu
6
*
CI
co
h v , NaOMe/MeOH,
36h
t
65°C
* Kashimura, T. ; Kudo, K.;
90%
285,
415
C O>
Buchan, C . : Hamel, N.; Woell, J.B.; Alper, H. Tetrahedron Lett, (1985), co2(co)8Y
3,293
20°C
Bumagin, N.A.; Gulevich, Yu.V.; Beletskaya, I.P. -J Organornet Chem, (19851,
R
86%
*
25°C
81 %
6'
26, 5743
95%
C02Me
Mori, S.: Sugita, N. 851
Chem Lett, (19861, --
Phi ( 0 2 C C F 3 ) 2
t
CH3(CH2)61 CHC13,
RT,
8h
Gallos, J.:
* Varvoglis, A.
CH3 ( C H 2 ) 6 c 0 2 c F 3
dark 43%
JCS Perkin I, (1983), 1999 ---
SECTION 116
ESTERS FROM H A L I D E S
157
6.
1. nBuLi 2. Z n C 1 2 CI
0
\/\\
C02Et
3. Ni(acacI2, 4.
CyPPh2
0
BrCH2C02Et
Klingstedt, T.; Frejd, T.
*
6 5%
-\
Organometallics, (19831, 2, 598
Previtera, L.; Monaco, P.; Mangoni, L. Tetrahedron Lett, (19841,
98%
25, 1293
*
82%
Hirao, T. ; Harano, Y.; Yamana, Y.; Hamada, Y.; Nagata, S.; Agawa, T. B u l l Chm Soc Jpn, ( 1 9861, 59, 1341 --Related Methods: Carboxylic Acids from Halides (Section 25) SECTION --1 1 6: Esters from Hydrides
This section contains examples of the reaction RH R'COOR (R = alkyl, aryl, etc.).
+
RCOOR' or
158 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
*
Heumann, A. ; Akermark, B.
*
SECTION 1 1 7
95%
--Int Ed x , (19841, 23, 453
Angew Chem
D D Q , AcOH OAC
RT,
Guy, A.;
Bouquet, M.;
20h
\
84%
Lemaire, M.;
Guett;,
J.P.
(19851, 15, 1153
=Camnun,
Also via: Carboxylic Acids (Section 26); Alcohols (Section 41
SECTION 1 1 7: -Esters from Ketones --m
S
e
0
2
H
H202,
Taylor, R.T.
0
CH2C12,
* : Flood,
72h
* 98%
J Org Chem, (19831, 48, 5160
L.A.
1. MeTi(OiPr)2, 20°C,
THF
*
2h
2 . HC1/PhCH3 3 . TBAF,
THF,
reflux
Kostova, K.: Hesse,,M.* Helv C h i m Acta, (1983), 66, 741 Hel=ifiActa,1984), 3,1448 Aono, T. ; Hesse, M.
---
54%
SECTION 117
1 . Me3SiOOSiMe3,
0 II
CH 3 (CH 2 I S C C H 3
SnCl
Matsubara, S.: Takai,
* K. ; Nozaki,
C H (CH ) 50Ac
6 9%
H.
Bull Chem Soc *,(19831, 56, 2029 ---
1. PhI(OAc)2,
H2S04
, 6OoC
HC(OMe)3 2.
25°C
*
2 . a q . Na2S203
Q
159
ESTERS FROM KETONES
HOH
8 5%
*
Tamura, Y. ; Shirouchi, Y.; Haruta, J. 1 . AcOH, 2 . HgO,
aq. acetone 1 2 , Py,
3. hv
4 . !Bu3SnH,
*
.
PhH,
PhH RT
Tetrahedron E,(1985),
Suginome, H. ; Yamada, S. 1
Synthesis, (1984), 231
T 1 ( N 0 3 ) 3 , TMOF MeOH,
O"C,
62%
26, 3715 C0,Me
30 m i n
2. a q . Na2C03
Mincione,
* E. ; Bovicelli,
P.: Gil, J.B.; Forcellese, M.L. --Gazz Chim Ital, (19851, 115,37
71 %
SECTION 1 1 8
160 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
* 8 0
1 . CH2=CHCH2CH2MgBr
2. [bipyH2]CrOC15 CHC13,
6h
50°C,
*
Rathore, R.; Vankar, P.S.; Chandrasekaran, S.
--
7 6%
Tetrahedron Lett, ( 1 9861,
0
CH2=CHC02Et,
II
PhCCH3
3,4079
THF
S m 1 2 , L B u O H , RT
t
3h
*
7 0%
Fukuzawa, S. ; Nakanishi, A.; Fujinami, T.; Sakai, S. JCS Chm C m , (19861, ---
624
Also via: Carboxylic Acids (Section 271
SETION 118: Esters from Nitriles
--
OH
I
-nC3 H 7 C H ( C H 2 ) 3 C N
a q . NaOH
r e f 1ux 12h
*
Giese, B. ; Hasskerl, T.; Liining, U.
Chem Ber, (19841,
-_.
*nC 3 H 70
0 80%
117,859
SECTION 119
161
E S T E R S FROM O L E F I H S
SECTION 119: -Esters from Olefins
AcOH,
F r i s t a d , W.E.
* ; Peterson,
OAc
AcO
2 5 % Mn(OAc)2
*
90°C
d-L
(meso:d,l
J.R.
49%
= 32:68)
Tetrahedron E ,( 1 983),
2,4547
5 [bipyH2]CrOC1 CH2C12, 40°C 8h
Chakraborty, T.K.;
Chandrasekaran, S.
*
80%
Tetrahedron Lett, (19841, 551
Chem Lett, --
(m),
3, 2895
1 . PPh3, Rh2(0Ac)4
Bno+l
HO
Wuts, P.G.M.
* ; Obrzut,
EtOAc,
'bomb'
CO/H2, 1OO"C,
6h
2 . PCC,
350 p s i
H i
O ;+ Q
0
CH2C12, R T
M.L.; Thompson, P.A. Tetrahedron E ,(19841,
86%
25, 4051
1 . C H 3 M n ( C 0 ) 5 , THF
3 . 9 KBar,
25°C
H
2 . L i B E t 3 H , -78°C DeShong,
* P. ; Slough,
H 0 G.A.
Organometallics, (1984),
44%
2, 636
162 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 OH
I
SECTION 120
\
PdC12, C u C 1 2
CH3CHCH=CHCH3
t
THF, HC1, C O / O ,
Alper, H.
*;
-
Tetrahedron Lett, ( 1 985),
Leonard, D.
'1
C3H7
M ~ ( O A C ) ~AcOH ,
C3H7
K2C03, r e f 1 u x
Fristad, W.E.
0 0
C3H7 -t C3H71"'
2h
C3H7
.+
(3.3
* ; Peterson,
0 C3H7
J Org Chem, (19851,
J.R.
26, 5639
0
50, 10
1 . SnC14, PhCH3 -29
Denmark, S.E.
*
-
O"C,
3h
2 . ta1nyl0-K'~ -70°C 3 . HC1 , C H ,LO
; Dappen, M.S.; Cramer, C . J . J Am Chem Soc, (1986), ----
Also via: Alcohols (Section
I
,. n,
4Uk
108,1306
44)
SECTION 120: -Esters f m Miscellaneous Canpounds
1. n B u 3 S n H , AIBN PhH,
reflux, 4h
2 . a q . HC1, C r 0 3
*
0
RT 80% * Stork, G. ; Mook J r . , R . ; B i l l e r , S.A.; Rychnovsky, S.D. ---J Am Chem Soc, (1983), 105, 3741
60%
E,STERS F R O M MISC.
SECTION 120
1. LDA,
163
T H F , -42°C
2 . PhCH2Br
o c I d 04
3 . NBS, C H 2 C 1 2
PPh,
>
PhCH2CH2C02Et 82%
E t.20
*
Liebeskind, L.S. ; Welker, M.E.; Fengl, R.W. ---J Am ChemSac, (1986), * Liebeskind, L.S. ; Welker, M.E. Organmetallics, (19831,
108,6328 2,
194
1. nBuLi
i e p /o\ 2*
0
Ph,P
, BF3
60%
3 . Br2
*
(RRS,SSR:RSR,SRS:RSS,SRR
Davies, S.G. ; Warner, P.
= 88:8:4)
Tetrahedron E,(1985),
26,
4815
0
PhSSPh
C O ~ ( C O ) ~P ,h H
58 a t m . C O Y 185'C
Antebi S. ; Alper, H. ~
*
*
Tetrahedron E,(1 985) ,
Ii
PhSCPh
69%
26, 2609
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 9 PREPARATION OF ETHERS, EPOXIDES, AND THIOETHERS
SECTION 121: Ethers, Epoxides, and Thioethers from Acetylenes
Ph
HCsCCH2CH20Ac
220°C, 48h
*
AcOCH CH
'
'h '0'
70%
Liotta, D.*; Saindone, M.; Ott, W. Tetrahedron Lett, (1983), 24, 2473
-
SECTION 122: Ethers, Epoxides, and Thioethers from Acid Derivatives
-
No Additional Examples and Thioethers from Alcohols SECTION 123: Ethers, Epoxides, Thiols
6
*
Kimura, Y.: Kirszensztejn, P.; Regen, S.L. -J Org Chem, (19831, 48, 385
and
SECTION 123
ETHERS FROM A L C O H O L S
$
165
nBuSH, 0 . 5 Z n 1 2
BU
$Bu
DCE, RT, 8 h
*
90%
*
Cuindon, Y. ; Frenette, R. ; Fortin, R.; Rokach, J. --J Org Chem, (1 983), 48, 1357 PhCl
,
hv,
2h
>
Me2CHCH2CH20H 2
* T.R. ; Adkins,
4-1
90%
0
Beebe, R.L.; Bogardus, C.C.; Champney, B.; Hii, P.S.; Reinking, P.; Shadday, J.; Weatherford 111, W.D.; Webb, M.W.; Yates, S.W. -J Org Chem, (1983), 48, 3126
K Y - z e o l i t e , 5h
* Onaka, M. ; Kawai,
6 9%
hexane, r e f l u x
M.; Izumi, Y.
Chem Lett, --
(19831, 1101
C 1 3CC02Me, BnCl
(K2C03/18-crown-6)
P
150°C
*
Renga, J.M. ; Wang, P.-C.
SynCamrun, (19841,
85%
14,69
166 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 123
0
0::; I1
*
HO( C H ) C H C H 2 0 H
91
OH
2 . NaOMe, MeOH
Bhat, K.S.; Joshi, P.L.;
PhCH20H
, AcOH
Rao,
* A.S.
PhSeH, ZnC12 DCE, 8 O o C , 6 m i n
Clarembeau, M . ; Krief, A.
*
/O\
HO(CH~)~CHCH~ 47%
Synthesis, (1984), 142
PhCH2SePh
t
*
Tetrahedron Lett, ( 1 9841,
81 %
25, 3625
*
Robinson, P.L.; Evans Jr., S.A. J Org Chem, (19851, 50, 5007 Robinson, P.L. ; Barry, C.E. ; Kelly, J.W. ; Evans Jr., S.A. J Am Chem Soc, (19851, 107, 5210 ----
Kelly, J.W.:
Diab, J . ; Abou-Assali, M.:
*
Gervais, C . ; Anker, D. Tetrahedron E,(1985),
8 9%
26, 1501
SECTION 124
167
ETHERS FROM ALDEHYDES
0
II
MeOCOMe , K2C03 18-crown-6, 8h
*
40%
Lissel, M. ; Schmidt, S . ; Neumann, B.
Ph3B:(OAc)2
RT, i
Synthesis, (19861, 382
*
Cu
CH2C12,
Barton, D.H.R.
+
1O O O C
5h
84%
; F i n e t , J.-P.: Khamsi, J . ; Pichon, C. Tetrahedron Lett, (1986), 3,3619
OH
I
PhCHCH20H
(tBuCH20)2PPh3 ..
CH2C12, 4OoC, 2 4 h
0
*
/I PhCHCH2
95% K e l l y , J.W.;
-J Org Chem,
Evans Jr., S.A.
Epoxides, SECTION 124: -Ethers 9
-
CHO
t
(19861,
51, 5490
"hioethers from Aldehydes
-
( Pr)2Te-CHCH=CH2 THF,
57%
-78OC
( Z-: E- = 8 0 : 2 0 )
Osuka, A.; Suzuki, H.
-
-
Tetrahedron Lett, (19831, 24, 5109
168 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 1. 5 CBuLi, 2. CH3CHBr2
PhCHO,
SECTION 125
- 1 1 5OC
0
-9OOC
/ \
t
3. L i O E t
PhCHCHCH3
(L:&=
4 . HOH
59%
2:l)
Tarhouni, R.; Kirschleger, B.: Villieras, J. J 0re;anomet Chan, (19841, 272, ci Tarhouni, R. ; Kirschleger; B. ; Rambaud, M. ; Villieras, J. Tetrahedron=, (19841, 25, 835 7. PhCH=CHCHO
(L)
6
Ph(CH2)30TMS 5% TrC104,
PhCH=CHCH20(CH2)3Ph
O°C
(r)
CH2C12, 5 m i n 2. EtgSiH, 5 m i n
Kato, J.; Iwasawa, N.; Mukaiyama, T.
NO2
1. Me3SiI,
2.
HOH,
Rafizadeh, K.: Yates,K.
Chem Lett, (19851, 743
50% NaOH
C H 2 C 1 2, B u 4 N I ,
88%
r e f 1 ux
-Q \
5°C
NO2
7 5%
Org Prep Proc Int, (19851, 17, 140
125: E t h e r s , Epoxides, Thioethers from Alkyls, SECTION Hethylenes, and Aryls 1. Hg(0Ac)2,
2'
0,
CH3CN,
Lee, T.D.: Daves Jr.,
HC104,
OMe
MeOH
Pd(OAc)2
24"C,
24h
* -J Org Chem, G.D.
(19831, 118, 399
80%
SECTION 128
169
ETHERS FROM ESTERS
SECTION 126: E t h e r s , Epoxides, and Thioethers from Amides
--
No Additional Examples SECTION 127: Ethers, Epoxides, NH2
1 . a q . H2S04 2 . NaN02,
O O M e
Baleja,
and Thioethers -from Mines
* J.D.
HOH,
22OC
3 . CuSMe
*
OMe
60%
2 SCarmun, (19841, 14, 215 h v , MeOH .2M H2S04
42%
pH 0 . 3
Scholl, B.: Jolidon, S.; Hansen, H.-J. Helv Chim Acta, ( 1 986), ---
and Thioethers
lo?
SECTION 128: Ethers, Epoxides,
2, 184
from E s t e r s
0.25 BF3*0Et2
CH2C1 2 , - 1 5°C
12h
x
Corey, E.J. ; Raju, N.
Tetrahedm
E ,(1983),
7 5%
2,5571
Ph
170 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 129
SECTION 129: Ethers, Epoxides, and Thioethera -f m Ethers, Epoxides, and Thioethers
--
,OMe
1 . EBuLi, T H F , 2. BnI
M e O e Ph
-4°C
t
Cr(co>3 3 . 02, Et20 65-80% * Davies, S.G. : Holman, N.J.; Laughton, C.A.: Mobbs, B.E. JCS Chem C a m , (19831, 1316
---
( C O ) 5w=c,
/(y H
*
-78°C
-
>
RT
90%
Fischer, H. ; Schmid, J . ; Miirkl, R.
JCS Chem Camn, ---
,
Et3A1
PhCH3,
Posner, G.H.
* ; Haines,
25°C
20h Murai, T.
10 min
7 9% 20:l) Tetrahedron Lett, (19851, 26, 1823
S.R.
Et2MeSiO(CH2)4fHOSiMeEt2
t
(62)
Et2MeSiO(CH
: Hatayama, Y.; Murai,
Murai, T . ; Furuta, K.:
0°C
(a:B =
HS i M e E t 2 PhH,
( 1 9851, 572
S.*:
+
CH3
77%
) CHCH20SiMeEt2
2 31
(38) CH3 Sonoda, N.
Organometallics, (1983), 2, 1883
Kato, S. Chem, (19861, -J Organomet -
302, 249
SECTION 130
171
ETHERS F R O M H A L I D E S
1 . Br,.
CC1
..
Et20, O°C
21
-
reflux
*
Davies, S.G. ; Polywka, M.E.C.: Thomas, S.E. JCS Perkin I, (19861, 1277 --SECTION 130: Ethers, Epoxides, Sulf onates iPrS-Na',
and Thioethers from Halides and RT
*
PhCH=CHBr
(L)
HMPA, 0.5h
* * Tiecco, M. ; Testaferri, L. ; Tingoli, M.;
Montanucci, M.
66%
PhCH=CHSiPr 95% (98%
r)
Chianelli, D.;
--J Org Chem, (19831, 9, 4795
0 II
MeSCSMe, 4 5 m i n
2 fiC8H17Br
B u d N B r , r e f 1 ux 30% a q . KOH
Degani , I.; Fochi , R. ; Regondi , V.
Brunelle, D.J.
*
J
Org
Chem, (19841,
*
2 CH3Sn-C8H17
quant
Synthesis, (19831, 630
9, 1288
I
172 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
nBu3SnCH20Me, H M P A PdCl 2 ( P P h 3 ) 2 , 180°C
SECTION 130
-*
70h
80%
*
Kosugi, M.; Sumiya, T.: Ogata, T.; Sano, H.; Migita, T. Chm L e t t , (1984), 1225
--
(Me3S i ) 2 S
B r ( CH2) 6 B r
2 M e L i , THF reflux,
Steliou,
* K. : Salama,
6h
61 %
P.; Corriveau, J. -J Org Wen, (19851,
2,4969
S
II
1 . Me2NCNMe2, D M F -
E t I
2 . BnOH,
DMF, NaH
+
E tSCH2Ph
76%
Fujisaki, S.: Fujiwara,
1 I
* I.; Norisue, Y.; Kajigaeshi, S. --Bull Chem Soc JJ, ( 1 985), 58, 2429
b S e - N a t ,
EtOH
( b i p y ) 2 N i B r 2 , 120°C 30h
Cristau,
* H.J. ; Chabaud,
B. * ; Labaudiniere,
90%
R.; Christol, H. Organomtallics, (19851, 2, 657
SECTION 132
E T H E R S F R O M KETOI4ES
173
Review: "Copper Assisted Nucleophilic Substitution of Aryl Halogen"
Lindley, J.
*
Tetrahedron, (19841,
40,
1433
Related Methods: Ethers from Alcohols (Section 123) SECTION 131: Ethers, Epoxides, and Thioethers from Hydrides
No Additional Examples SECTION 132: Ethers, Epoxides, a&l
Thioethers fran Ketones
26)
(74
Garst, M.E.*; McBride, B.J.: Johnson, A.T.; Arrhen .us,P. -J Org Chm, (19831, 2, 8 16
-w 0
@ ,,""
I
I1
3 CH3SCH2Na II
N-RT s
7i%
/ \ DMSO, 45°C (88 12) Welch, S.C.*; Prakasa Rao, A.S.C. ; Lyon', J .T.; Assercq, J .-M.
J Am Chem Soc, ----
CH3CH(OEt)2
PhCu, -3O"C,
LiCl 30 min
Ghribi, A,; Alexakis, A.*; Normnt, J.F. Tetrahedron Lett, ( 1984),
(19831,
105, 252
b
PhCHOEt
89%
3, 3075,
3079, 3083
174 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 132
1 . mcpba 2.
Dibal-H,
3 . Hg0-12, 4. 5. 6.
hv,
I2
*
n
*
2 . a q . NaOH
*
Bailey, W.F. ; Bischoff, J.J.
Me
Ph
44%
-
J Org Chem, (1985),
1 . C H =C'CH2MgC1 /Me
50,
3009
QSMe
2 . THF:HOH 1 0 % HBF4 80%
* Dieter, R.K. ; Lin, Y.L.
-o..ll!~:
25, 3995
(1984),
CH2C12
r e f l u x , 8.5h
0":
3 9%
reflux
Tetrahedron=,
1 . rncpba,
U
*/
PhH
3h
N a B H 4 , THF,
Sugincxne, H. ; Yamada, S. EtQ Q E t
-78°C Py,
Tetrahedron =,(19851,
1. Dibal-H,
THF,
2 . LiA1H4
a
3 . Me O + B F ~ 4 . Na H
Salladie, G.*; Demailly, C.; Greck, C.
26, 39
-78OC I
-
\
ttt~~~H
95%
Tetrahedron E,(19851,
Ph
26,
435
SECTION 134
Sadhu, K.M.:
ETHERS F R O M OLEFINS
Matteson,
* D.S.
175
91 %
Tetrahedron E,(19861,
Me6Me Nafion-H , h e a t E t 3 S i H , CH2C12, 2 h
*
2,795
e J.\
\
* ; Yamato,
Olah, G.A.
T.; Iyer, P.S.: Surya Prakash, G.K. -J Org Chem, ( 1 9861, 51, 2826
Review: "Recent Advances i n the Preparation and Synthetic Applications of Oxiranes"
*
Rao, A.S. ; Paknikar, S.K.: Kirtane, J.G. Tetrahedmn, (l983),
3,2323
Related Methods: Epoxides from Aldehydes (Section 124)
SECTION
133: Ethers,
Epoxides, and Thioethers from Nitriles
No Additional Examples SECTION
9: Ethers, Epoxides, and Thioethers from Olefins CH2=CHCH2TMS, PhSCl
ZnBr2, CH3N02, 2 0 ° C 16h Alexander, R.;
Paterson,
* I.
t
Tetrahedron E, (1983),
78%
211, 591 1
96%
176 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
,
&A,Cl
KO2,
SECTION 134
CH3CN
4.5h,
-35'C 87%
K i m , Y.H.
* ; Chung,
B.C.
JJ Chen,
NaW04.2H20,
70"C,
4 0 % H3P04,
8% a q .
30% H2S04,
45 rnin
(19831,
48,
1562
DCE
H202
(._?-C8Hl 7 ) 3 N M e C 1
81 %
*
Venturello, C. ; Alneri, E.: Ricci, M. -J org Chem, (19831, 1 . Cr02(N03)2,
48,
3831
l h
DMF-CH2C1 2 , - 7 8 ° C 2 . 1 0 % a q . NaHC03
Miyaura, N. ; Kochi, J . K .
* ---J Am Chm Soc,
51 X
(19831,
105,2368
Me c a t . P h - C - N = N Q1B r\ I
OOH
a q . NaOH,
Tezuka,
* T. ; I w a k i ,
d i o x a n e , RT 12h
M.
Jcs Perkin
t
77%
I , (19841, 2507 H e t e m e z , (19841, 22, 725
ETHERS FROM O L E F I N S
SECTION 134
N
\-I
~
N
177
~ 30% H202 ) .
CH3CN:CH2C1 2, r e f l u x
91 %
Mn(TDCPP)Cl TDCPP = t e t r a - 2 , 6 - d i c h l o r o p h e n y l
Renaud, J.-P.:
porphyrin
Battioni, P.; Bartoli, J.F.: Mansuy, D. JCS Chem C a m , ( 1 985), 888 --0
1 0 % ( PPh3Bn)2W201 CH3(CH2)9CH=CH2
DCE,
t
30% H202,
4OoC,
/ \
CH3(CH2)9CHCH2
24h
Prandi, J . ; Kagan, H.B.; Mimoun, H. Tetrahedron E,(19861, Mn(TFPP)Cl CH3 ( CH2 ) 5CH =CH2
,
KHS05,
70%
3, 2617 0
RT
BnCH2NMe2C14H29C1
CH3(CH2)5CHCH2
C H 2C1 2, Na 2 H P O 4
TFPP = 5 , 1 0 , 1 5 , 2 0 - t e t r a
De Poorter, B.; Meunier, B. cat.
L-M,
= ( n B u N ) HMPW11039
Hill, C.L.
14
61 %
luorophenyl porphydrinato-2 P e r fNouv J Chem, (19851, 9, 393
CH2C12,
1-M
4
; Brown J r . , R.B.
PhIO,
24OC
2h M = Co J Am Chem Soc, (19861,
M = Fe ( c y c l o o c t e n e )
Groves, J . T .
1
; Nemo, T.E. J Am Chem
__--
1 '\
Soc, (19831,
82%
108,536 84%
105,5786,
5791
178 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
, 25°C
PhCl
10
Pti
P h - f - 0 - Mn- 0- I - P h OAc
A p%
>
+
Ph
I
Smegal, J.A.; Hill, C.L.
OAc
* ---J Am Chem Soc,
*
Edstrom, E.D.; Livinghouse, T. Tetrahedron :lo,, pJ+
0
Z0,S'
CHC13,
(19831,
Ar H
25OCY 48h
*
7 Ph
Rozen,
* S. ; Brand, M.
105,2920
(53% ee)
Tetrahedron E ,(19861,
N2/F2'
L
-15OC
a q . CH3CN
h
Ph 73%
Ph
: Chattopadhyay, S.
Ph
Ph
E ,(19861, 3, 3483
Z (-)-3-bromocamphor A r = 2-chl$ro-5-nitrophenyl
Davis, F.A.
SECTION 134
*
60-70%
3, 5079
Ph
Angew Chem Int Ed Engl, (1986),
8 0%
Ph
3,554
Review: "Preparation and Synthetic Applications of Oxiranes"
*
Rao, A.S. ; Paknikar, S.K.; Kirtane, J . G . Tetrahedron, ( 19831,
3,2323
179
E T H E R S FROM M I S C .
S E C T I O N 135
SECTION 135: Ethers, Epoxides, and Thioethers from Miscellaneous canpounds
*d
1. BF3*0Et2
"x"
2 . THF, 3.
Meltz, C . N . ;
I1
6-Br,
-23
* Y. ; Atkinson,
0 II PhCH 2 S P h
@
-
30
-
O"C,
*; Kim,
J.E.;
-
t
,
-J Org
3,4538
t
PhCH2SPh 93%
Kim, J.D. Tetrahedron Lett, ( 1 985),
THF/CCi 4 y
*
90%
CH2C1
,
26, 6453
r e f 1ux
1 .5h
t
nBuSlBu
9 %%
= polystyryl
Amos, R.A.
PhCH2SCH3
0°C
10 min
@PPh2C1
3, 4507
CH2C12
J . G . : Morton, H.E. J Org Chem, ( 1 9841, ---
I-+-BHCl
0 II n BuSnB u
80%
Tetrahedron Lett, ( 1 983),
PhCH2SCH3
C h a , J.S.
Ph
2h
CH2=C, OL i TFA:HOH
Volkmann, R.A.*
0
Guindon,
- 7P8h" C , /
Chem, (1985), 50, 1311
180 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 135A
PhS-Na', 50°C,
*
HMPA 2h 63%
Ono, N. ; Hamamoto, J . ; Yanai, T.: Kaji, A . JCS Chem Cam, (1985), 523
---
PhSS i M e 3 , S n C l
PhCHCH 2 C H
t
PhCHCH2CH3
I
2h
SPh
N02
Ono, N.
z
: Yanai,
Casey, C.P.
SECTION
T.: Kaji, A.
* ; Shusteman,
A.J.
71 %
JCS Chaa Cana, (19861, 1040
Ot'ganauetdllics,
(19851,
2,
m: Protection of Ethers, Epoxides, @ Thioethers
4
40% a q . CH3N02 30°C,
Doi, J . T . ; Luehr, G.W.
20h
--
74%
Tetrahedron E,(19851,
26,
61 43
736
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 10 PREPARATION OF HALIDES AND SULFONATES
SECTION
136: Halides and Sulfonates from Acetylenes No Additional Examples
SECTION 137: Halides and Sulfonates from Acid Derivatives
p
t
GC1 -
N-oNa
\
reflux
CC14,
c a t . DMAP
*
Barton, D.H.R.; Crich, D. ; Motherwell, W.B. Tetrahedron E ,(19831,
6"
PhN02,
15h
*
Uemura, S.; Tanaka, S.: Okano, M. -J Org Chan, (19831,
OMe
48,
-
6
3297
*
&O"
* Barton, D.H.R. ; Lacher, B.;
2,4979
36%
BrCCl 3, 100°C 30% A I B N
88%
Zard, S.-2. Tetrahedron Lett, (19851,
OMe 84%
26, 5939
182 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 138
COOH
P h I ( OAc) hv
Y
cc14 90 min
ACO""
80%
Concepci&, J.I.; Francisgo, C.G.; Freire, R . ; Hernandez, R.; Salazar, J.A. : Suarez, E. -J Org Chem, (1986), 51, 402 SECTION 138: Halides and Sulfonates from Alcohols -and Thiols un
n
c
n
Denis, J.N.: Krief, A.
I
r
*
JCS Chem Carm, (1983), 229 ---
M e S i C 1 3 , N a I , RT CH3CN,
I
15 min
*
HO
*
Olah, G.A. ; Husain, A.; Singh, B.P.: Mehrota, A. K. -J Org Chem, ( 1 9831, 48, 3667 -1OOC
3. distil
Hrubiec, R.T.;
* Smith, M.B.
'
DMF
1 . PPh3, 2 . Br2,
71 %
7 9%
-J Org Chem,
(1984),
9, 431
96%
SECTION 138
HALIDES FROM ALCOHOLS
w
OH
I
nC6H1 -
P
h
2
, 20°C
nC6H1 3CHCH3
CBr4, CHC13, 4 0 m i n
76%
* P. ; Khoshdel , E.
JCS Perkin I, (1984), 195
H(CH2CH2),,-CH2CH2PPh2
E c 7 H 1 5C H 2 O H
Br 11
3iHCH3
Hodge,
P
183
CC14, P h C H 3 ,
90°C
*
CH C1 EC7H15 2 96%
Bergbreiter, D.E.
* : Blanton,
J.R.
@C H 2 N R 2 / PhCH2CH20H
@=
JCS Chem Cam, (19851, 337
PB r 3
E t 2 0 , RT, l h
*
PhCH2CH2Br 82%
Amber1 i t e IRA93
Cainelli, G.; Contento, M.; Manescalchi, F.: Plessi, L.; Panunzio, M. Synthesis, (19831, 306
b
PSSE, NaI 10h, RT
PSSE = t r i m e t h y l s i l y l p o l y p h o s p h a t e
* Imamoto, T. ; Matsumoto,
-6 99%
T.; Kusumoto, T.: Yokoyama, M. Synthesis, (1983), 460
184 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
9"
TsC1,
DMAP, N E t 3
CH2C12,
'f'''81 OH
8'
*
24h
25OC,
SECTION 138
""'~"1
CI
Hwang, C.K.; Li, W.S.; Nicolaou, K.C. Tetrahedron Lett, ( 1 984), 1.
c 1, C = N P h 2 t P h'
C1
-
,
CH2C12,
85%
25, 2295
NEt3
RT
*
"C11 H 2 3 0 H
2 . HOH
"1
1 H23C1 96%
*
Fujisawa, T. ; Iida, S.; Sato, T.
Chem Lett, (19841, 1173
74% * Oshikawa, T. : Yamashita, M. will Chem Soc e, (1984), 57, 2675 --OH
I
nBuCH(CH2)9CH20H
a S 0 2 F Bu,NF,
THF,
RT
4A s i e v e , I d
OH
* *
I
nBuCH(CH2)9CH2F -
Shimizu, M.*: Nakahara, Y.; Yoshioka, H. Tetrahedron Lett, (1985),
69%
26, 4207
SECTION 139
HALIDES FROM ALDEHYDES
185
0
II
1 . ClCOCHClMe, N a I acetone, ref1 ux
CH3CH2CH2CH20H
2. PhCH3,
75OC
C I JCH2CH2CH21
*
65%
* P.
Brunet, J . J . ; Lament, H . ; Caubere, Tetrahedron Lett , ( 1 985) ,
-
2.45 DEAD,
2.5 PPh3
*
ArCH2CH20H
Ar
=
Manna, S . ; Falck, J . R .
Ar =
* : Mioskowski, Syn
C. Ccumnm, (19851,
95%
3,663
P y . H C l I C H 2 C 1 2 X = C1
c1
Alpegiani, M . ; Bedeschi, A . ; Perrone, E. Gazz C h i m Ital, (19851,
---
2 TMS-C1, C H 2 C 1 2 30°C, 90 m i n
*
5445
ArCH2CH2X
X = Br
5 LiBr/THF
Ph
26,
96%
115, 393
*
Balme, G. ; Fournet, G.: Gore, J. Tetrahedron Lett, ( 1 986) ,
-
90%
3, 1907
SECTION 139: Halides and sulfonates from Aldehydes ( H S i M e 2 ) 2 0 , MaI, O ° C PhCHO TMS-C1, C H 3 C N ,
Aizpurua, J . M . ;
Palorno,
* C.
30 min
* -
PhCH21
Tetrahedron Lett, (1984),
91 %
3, 1103
186 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 141 F
* Haas, A . ; Pliimer, R.:
43%
Schiller, A. Chem Ber, (19851, --
118,3004
-
SECTION 140: Halides and Sulfonates from Alkyls, Methylenes, and A r y l r -
For the conversion RH Hydrides).
* Ayorinde, F.O.
+
RHal see Section 146 (Halides from
2, 2077
Tetrahedron Lett, (19831,
60%
-
W . B r 2 , CC14 reflux, c a t . BnOOBn
zket, B.;
* Zupan, M.
J Org Chem, ---
(19861,
2,929
SECTION 141 : Halides and Sulfonates -from Amides
-
No Additional Examples
96%
HALIDES F R O M E T H E R S
SECTION 1 4 4
187
SECTION 142: Halides and SulfOMteS -from Amines
-
-
0
II
DCE
1 . C1CCHCH3,
c1 1
0°C 0
Olofson, R.A.
&N-(CH2)4C1
~
0
2. reflux 3 . MeOH, r e f l u x
*f
Abbott, D.E.
J Org
94%
Chem, (1984),
3, 2795
-
from Esters SECTION 143: Halides and Sulfonates --
No Additional Examples SECTION 144: Halides and Sulfonates from Ethers, Epoxides, and ThioetheT
Me3SiBr, Br2 t
50°C, 5 4 h
75%
*
Friedrich, E.C. ; DeLucca, G.
J Org Chem, (19831, -
1 . N a I , C1SiMe3, C H 3 C N (HSiMe2)20, r e f l u x
2. 4 5 % H F , r e f l u x
Aizpurua, J.M.; Palomo,
b
* C.
g, 1678
* 7 5%
Tetrahedron
E ,(1984), 25, 3123
188 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
( C F 3 S 0 2 ) 2 0 , 0°C
nBuOTMS
*
CH2C12, 1 5 m i n
Aubert, C . ; Be'gug, J . - P .
-
SECTION 145: Halides
*
Br
nBuOS02CF3 72%
Synthesis, (1985), 759
and Sulfonates from Halides and Sulfonates
1 . TMS-C1, N E t 3 , RT, l h 2 . Na, Ne3SiC1
"0
SECTION 145
THF
*
3 . A c 2 0 , Py 4 . NCS, N a I , 6 0 ° C AcOH, l h
76%
* Wilbur, D.S. : Stone, W.E.; Anderson, K.W. --J Org Chem, (1983), 48, 1542 Br
L i A 1 H 4 - 1 % AgC104
Br T H F ,
*
-20°C
*
t
5 9 % (-Z :-E = 8 : 1 ) 0%
THF, l h T H F , 24h
Shimizu, N. ; Watanabe, K.; Tsuno, Y. 0 1 I 4 H P ( O E t ) 2 , 90°C
2 NEt3,
(yBr 0
20h
35% 77%
Chem Lett, (19831, 1877
*
H
76%
Hirao, T. ; Kohno, S.;
Ohshiro, Y.*; Agawa, T. --Bull Chem Soc (1983),
s,
56,
1881
SECTION 145
*
189
H A L I D E S FROM H A L I D E S
94% (E : Z- = 7 2 : 2 8 )
Osuka, A . ; Takechi,
* --Bull Chem Soc s,(1984), 57,
K.*; Suzuki, H.
303
KF
-n C 8 H 1
t
7C1
._?.'gH17 F
Bu4NBr
69%
Escoula, B.; Rico, I.: Lattes, A.
Tetrahedron Lett, (19861,
3, 1499 F
CI
A
I
CH2C12,
0°C
5h
*
r
9 5% Olah, G.A.*;
PhCH2Br
Singh, B.P.; Gupta, B.G.B. Synthesis, ( 1 983) , 71 3
Shih, J . G . ;
KF-CaF2 CH3CN,
(1 : 2 ) reflux, 15h
*
PhCH2F 81 %
Ichihara, J.
* ; Matsuo,
T.; Hanafusa, T.: Ando, T. JCS Chem Comn, (19861, 793
---
190 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Bu4NF *3H20 CH2=CHCH2Br
>
SECTION 146
CH2=CHCH 2F
vacuum, 48h Cox,
* D.P. ; Terpinski,
J . ; Lawrynowicz, W.
J Org Chem, (19841, ---
a 5%
9, 3216
KI, C u I HMPT,
16OOC
7h
Suzuki,
* H. ; Kondo,
80%
Inouye, M.: Ogawa, T. Synthesis, (19861, 121 * Suzuki, H. ; Kondo, A . ; Ogawa, T. Chem Lett, (19851, 41 1 A.;
Review: l'Radical Brorninations of A l k y l Bromides and the Nature of B-Brornoalkyl Radicals" S k e l l , P.S.*; Traynham, J . E .
*
Accts Chem Res, (1984),
17,160
SECTION 146: Halides and Sulfonates from Hydrides
a-Halogenations of Aldehydes, Ketones, and Acids are found i n Sections 338 (Haloaldehydes), 369 (Haloketones), 359 (Halo-Esters), and 319 (Haloacids).
Lindsay-Smith, J . R .
OMe
OMe
OMe
CI
* ; McKeer,
L.C.
1%
99%
Tetrahedron E ,( 1 9831,
24,
31 17
HALIDES FROM KETONES
SECTION 147
191
F
NOtBF4- , 6h PPHF, CH2C12, RT
95% PPHF = pyridinepolyhydrogen fluoride * Olah, G.A. ; S h i h , J.G.: Singh, B.P.: Gupta, B.G.B. -J Org Chem, (19831, 118, 3356 0 II
1 . CH3COF, CH2C12, CFC13 -75°C
F
H
2.
HOH
Lerman, 0 . : Tor, Y.: Hebel, D . : Rozen, S." J Org Chem, (1984),
-
tBuOCl
, Si02, CC14
RT, lh quant. [Zeolite, NaCl, 40"Cl
Smith, K .
SECTION
* ; Butlers,
-
-
(0:p
M.; P a g e t , W.E. Synthesis, (1985), 1155, 1157
CnC H "C5H11 -
1 . HS(CH2)3SH, B F 3 2 AcOH 2 . DBH, 20 PPHF CH2C1 * , -78°C
*
85%
3,806
=
= 65:35) 82:18]
1117: Halides and Sulfonates prom Ketones
0
II
( 0 : e= 9:l)
F 1
!c5H11f!C5H11
F
97 % DBH = 1 , 3 - d i b r o m 0 - 5 , 5 - d i m e t h y l hydantoin PPHF p y r i d i n i u m poly(hydro e n 3 f l u o r i d e Sondej, S.C. ; Katzenellenbogen, ?.A. J Org Chem, ( 1 9861, 51, 3508
192 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION
SECTION 150
1118: Halides and Sulfonates prom Nitriles No Additional Examples
SGTION
3: Halides
Sulfonates
prom
Olefins
For halocyclopropanations see Section 743 (Alkyls from Olefins). S0,CI
CH2=CHPh,
c1
PhH
> 4 % Ru2C1 0 4 ( d i o p ) 3 6Q°C, I h
Kameyama, M.:
PhtHCH2SO2O 92%(49%conversion)
* Kamigata, N. ; Kobayashi, M.
(29% e e R )
-Chem Lett, (1986),
1 . BEt3' RT,
"C, O H 2 1 C H = C H 2
C12A1H 2h
2 . 1 2 ' Py, -78°C lh
-
527
"C1 OH21 CH2CH2I
85%
Maruoka, K.: Sano, H.; Shinoda, K.; Nakai, S.; Yamamoto, H. J Am Chem Soc, (1986), 108,6036 ---SECTION m : - H a l i d e s
*
and Sulfonates from Miscellaneous Compounds TMS- I
CH2C1
25"C, 16h 3c
Olah, C.A. ; Narang, S.C.; Field, L.D.; Fung, A.P. J Org Chem, (1983), 118, 2766
98 %
HALIDES FROM M I S C .
SECTION 150
193
Q
N=N-NE t
I
A G 50W-X12 B i o r a d (H')
NaI,
CH3CN,
Satyamurthy, N . ; Barrio, J . R .
0
It
CH SePh nCgH19 2,,
0
Krief,
* A . ; Dumont,
*
2 NaI,
acetone,
5
t
min
90%
J Org Chem, (1983),
48,
4394
20°C l h
t
E C g H 1 9C H 2 I 97%
W.;.Denis, J.-N. JCS Chem C a m , (1985), 571
---
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 11 PREPARATION OF HYDRIDES
This chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogens, e.g. RCH,X + RCH,-H
or R-H.
SECTION
151: Hydrides from Acetylenes No Additional Examples
SECTION 152: Hydrides -from Acid Derivatives
This section lists examples of decarboxylation (R-COOH and related reactions. 1. CI
Barton, D.H.R.
Ph,
70% D . ; Motherwell, W.B.
JCS Chem C a m , ---
( 19831,
939 NHAc
ph'C=(
*
COOH
PY/CU
67%
Q u in o 1 in e / C u
*
R-H)
PhH, 8OoC
,NHAc
,c =c,
H
* ; Crich,
+
75%
Schmidt, U. ; Lieberknecht, A.
H'
H
(Z:E
= 84:16)
(Z:E
= 16:84)
-
-
c
c
Angeu Chem Int Ed Engl, (1 983),
22,
550
SECTION 153 COOH
CH3CN,
HOH,
Fristad, W.E.*; Fry, M.A.
P
52%
,’ Klang, J.A.
48,
J Org Chem, (1963), Cu20,
0
reflux
Na2S208
3575
50°C
CH3CN
COOH
Toussaint, 0 . ;
195
HYDRIDES FROM ALCOHOLS
Capdevielle,
P.;
Maumy,
M.
Tetrahedron, (1984),
6..
quan t
110,
.
3229
SECTION 153: Hydrides Prom Alcohols and Thiols
-
This section lists examples of the hydrogenolysis of alcohols and phenols, ROH + RH. Fe3(COI1 PhH,
\
2 y
Bu4NHS04,
+
5N NaOH
60°C overnight
*
*
Alper, H. ; Sibtain, F.; Heveling, J. Tetrahedron Lett, ( 1 983), P214,
N2’
PhH
heat,
6h
boM 87%
*$ 2, 5329
84%
Suzuki, H.; Tani, H.; Kubota, H.; Sato, N.; Tsuiji, J.; Osuka, A. Chem Lett, (1983), 247 --
196 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 00
I1 I I
1. ClCCCl
2*
a,
DMAP,
Barton, D.H.R.
reflux
4 LBuSH,
. ..
(1984), 774
1 . ClCCOMe I1 I I
-
2 . Bu3SnH AIBN,
, ,
@ .
t PhMe AcO
r e f 1ux
Dolan, S.C.; MacMillan, J.
$"
cl
55%
l h
00
$
AcO
7
* : Crich, D. --JCS Chem C a m ,
@ ,
PhH,
to Na
~.
SECTION 153
.I
-> '
65%
W
JCS Chem C m , (19851, 1588
C O ~ ( C O ) ~ HOH/PhH ,
900 p s i CO,
\
190°C
*
Shim, S.C.: Antebi, S.; Alper, H. Tetrahedron Lett, ( 1 9851, 1.
S
PhCH,,
,
84%
26, 1935
Bu3P
r e f l u x , Sh
2 . Bu3SnH, A I B N PhH,
*
reflux,
14h
Watanabe, Y. ; Araki, T.; Ueno, Y.: Endo, T. Tetrahedron Lett, ( 1 986),
69%
27, 5385
SECTION 157
197
H Y D R I D E S FROM ALDEHYDES
Review: "Radical Deoxygenation of Alcohols"
Hartwig, W.
*
Tetrahedron, (1983), 3,2609
Also via: Halides and Sulfonates (Section 160)
-
SECTION 154: Hydrides from Aldehydes
H
\
/CHo
,C=C\Et fiC7H1 5
_c.
R h C l ( PPh3)3
EtCH=CHnC7H,
(I:E =
CH2C1 2 , 1 6 0 ° C
0.7h
30%
62:18)
+
EtCH2CH2nC7H,
20%
*
Grigor'eva, N.Ya.; Pinsker, O.A.; Semenovskii, A.V. will Acad Sci USSR, (1983), 32, 593 ---For the conversion RCHO from Aldehydes).
+
RMe, etc. see Section 64 (Alkyls
SETION 155: Hydrides from Alkyls, Methylenes, and Aryls No Additional Examples SECTION 156: Hydrides from Amides
-
No Additional Examples SECTION 157: Hydrides from Amines
-
This section lists examples of the conversion RNH,
-*
RH.
198 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Maier, W.F.
G u t t i e r i , M.J.;
SECTION 158
12%
88%
It
J Org Chem, (1984),
2,2875
SECTION 158: Hydrides from Esters
This section lists examples of the reactions RCOOR' RCOOR' .+ R ' H . LiC104
P h CH =C H C H O A c
(E) Nakamura, K.:
CH3CN,
+ (E)
*
RhCl ( PPh3)3
hu,
RH and
PhCH=CHCH3
dark
Ohno, A.: Oka, S. Tetrahedron
+
97%
PhCH2CH =CH2
z, 983), 24, 3335
5h
0.6%
(1
+
HMPT/HOH OAc
84%
Portella, C . ; Deshayes, H . ; Pete, J . P . ; Scholler, D. Tetrahedron, (1984), 40, 3635 Nickel boride ______)
d ig l y m e
10 min Nickel boride = [NiCl Sarma, D.N. ; Sharma, R.P.'
/NaBH4/diglyrne]
98%
Tetrahedron Lett, (19851,
26,
2581
SECTION 160
H Y D R I D E S FR0i.i
SM12, LBuOH
CH3
I
PhCH=CHCHOAc
THF,
RT,
(E-)
PhCH=CHCH2CH3 -b
lh
(83) 81 %
1% Pd(PPh3)4
Tabuchi, T.:
199
ETHERS
* Inanaga, J. : Yamaguchi, M.
( EtI)
P h CH 2 C H =C H CH
( 1 7)
Tetrahedron Lett, (19861,
27, 601
t B uO O t Bu Ph3SiH 140°C, Sane,
*
12h
H. ; Ogata, M.: Migita, T.
*
82%
Chem Lett, (1986), 77
--
SECTION 159: Hydrides -f m Ethers, Epoxides, and Thioethers This section lists examples of the reaction of R-0-R'
+
R-H.
SePh
THF/MeOH,
* Back, T.G.
O°C
15 min
JCS Chem C o ~ m ,(19841, ---
1417
93%
SECTION 160: Hydrides f m Halides and Sulfonates This section lists the reductions of halides and sulfonates, RX RH. -f
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
200
ur
"
Beckwith, A.L.J.
I
n B u CI - X -
X = C1, Kim,
Kim,
S.H.
E t I
>
nBuC-H I E t
Y.J.; Ahn, K . H .
Tetrahedron Lett, (1983), 24, 3369 95%
Syn Cornnun, --
J.S.
i
Et20,
* S. ; Hong,
PhCH 2 S C H 2 B r
C.Y.;
PhCH2Ph 99%
Yang, S.
hgew Chem Int Ed Engl, ( 1 983),
'gH14'
M.
t
0.2h
C O ~ ( C O ) ~A1, 2 0 3
* : Gopal,
3,603
(19851,
Zn(BH4)
PhCHPh
Alper, H.
Et20
M = Sn
* S. ; KO,
0 II
MC12],
96%
Br
Kim,
JCS Chem Cam, (1983), 907
M = Zn
* S. ; K i m ,
X = Br,
quant.
RT
2.5h,
E t
0Me
h..
"3"
* ; Goh,
[ 2 NaBH3CN,
Et
SECTION 160
RT, 2h
22,
0
I!
*
PhCH2SCH3 quant.
-
J Org Chem, (1983), 48, 4390
562
HYDRIDES F R O M HALIDES
SECTION 160
201
Br
Osuka, A . :
PhCCHCH3
78%
Chem Lett, (19831, 119
Suzuki, H.
1 . SnC12, 2 Dibal-H TMEDA, THF, PhCH3
I
-78"C,
Br
6
2 . pH 7
Oriyama, T.; Mukaiyama, T.
\
Boyer,
10 min
0
*
PhCCH2CH3
+
Chem Lett, (19841, 2069
NaH2P02, T H F , 65°C Na2C03, c a t . P d - C
* S.K. ; Bach,
II
81 %
\
HOH
96%
J . ; McKenna, J.; Jagdmann J r . , E.
-J Org Chem,
( 1 9851,
50,
3408
Br
NiC12, H O H ,
HMPA, Yamashita,
* J. ; Inoue,
NaI
60°C
o),>))
t
91 %
Y.; Kondo, T.; Hashimoto, H. wlll Chem Soc *,(19851, 58, 2709
---
202 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
tBuOOJBu, hw,
DMF,
NaBH4 80°C
SECTION 162
>
6h
74%
Abeywickrema, A.N.; Beckwith, A.L.J.
-
Tetrahedron Lett, (19861,
cat. PhCCH2Br
3, 109
P d ( P P h 3 ) 4 , 160°C
PMHS,
*
CH3CN/DMS0
Bn3N, 3h
PhCCH3 8 0%
PMHS = p o l y m e t h y l h y d r o s i l o x a n e
Pri-Bar, I.*; Buchman, 0.
OTf
J Org Chem, (19861,
51,
734
2% Pd(OAc)2, N E t 3 4% PPh3,
6OoC, l h
Cacchi, S.; Ciattini, P.G.; Morera, E.;
* Ortar, G.
-
Tetrahedron Lett, ( 1 9861,
91 %
3, 5541
SECTION 161 : Hydrides from Hydrides
No Additional Examples SECTION 162: Hydrides from Ketones
This section lists examples of the reaction R,CCOR
+
R,C-H.
SECTION 164
H Y D R I D E S FROM N I T R I L E S
203
5 CF3COOH, H O H b
reflux,
15h 93%
36
Keumi, T. ; Morita, T.; Inui, Y.; Teshima, N.; Kitajima, H. Synthesis, ( 1985), 979 SECTION 3: Hydrides from Nitriles
-8
This section lists examples of the reaction RCN 1 , K, PhCH3 18-crown-6 &N
-*
RH.
d i cR yT c l o h e x a n e 2 . HOH
*
95%
Ohaawa, T. ; Kobayashi, T.; Mizuguchi, Y.; Saitoh, T.: Oishi, T. Tetrahedron E, (1985), 26, 6103 SECTION 164: Hydrides from Olefins
No Additional Examples
204
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 165
SECTION 165: Hydrides from Miscellaneous Compounds
"10"2!
H
./
Oda, H.;
c =c
/
\
H
nBu4NF
S iMe2Ph
H M P A , 80°C 30 min
b
"1
OH21 >=cH2 CH3
77%
*
Sato, M.: Morizawa, Y.; Oshima, K. ; Nozaki, H. Tetrahedron Lett, (1 983), 24, 2877
NaHTe, RT,
EtOH
1 5 rnin
*
85%
Suzuki, H. ; Takaoka, K.; Osuka, A. W 1 Chem Soc .7pn, (19851, 58, 1067
---
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 12 PREPARATION OF KETONES
SECTION 166: Ketones from Acetylenes 1. HSiMe(OEt)2 2 . H2PtC1 6 * 6 H 2 0 RT,
nBuC=CnBu
30 m i n
3 . 30% H202, KHCOQ
*
nBuCH2CnBu 82%
r e f 1 ux
t.:eOH/THF,
*
0
It
Tarnao, K. ; Ishida, N.; Tanaka, T.; Kumada, M. Organometallics, ( 1 983 1,
2, 1694 0
1 . HgC12, K2C03 BnOCH2CnCH
THF,
t
RT
2 . H30+
*
6 0%
Barluenga, J. ; Aznar, F.; Liz, R. 1.
Q Ph'
nB u C s C H
* Yamashita, A.
95OC,
Synthesis, (19841, 304
C=Cr (CO)
DWF, 1 2 5 " C , 2.
II
BnOCH2CCH3
15h
5h
>
WBU 0
95%
Tetrahedron E,(19861,
3, 5915
206 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 167
SECTION 167: Ketones fnw Acid Derivatives
-
35%
*
Tetrahedron
Chou, T.-S. ; Huang, S.-B.
PhMgX, THF
CH3CH2CH2COOH
e, (19831, 24, 2169 0
It CH3CH2CH2CPh
*
Ni ( d p p e ) C l
65%
r e f 1 ux
Fiandanese, V.; 0
II
PhCCl
Marchese, G.*; Ronzini, L. Tetrahedron E ,(1983), PhCH2C1 , g l y m e , 8 5 O C
Inaba, S.: Rieke, R.D. 0
0
+
*
J Org Chm, (1985),
-
PhCH2CPh
25'C,
6h
5% P d ( P P h 3 ) 4
2,1373
73%
OYPh
C l e Z n C l , THF
PhCCl
11
45 min
Nio,
II
2, 3677
-+ CI -.
* Negishi, E. : Bagheri, V.;
J . A . ; S t o l l , A.T.
95%
Chatterjee, S.; Luo, F.-T.; Miller,
Tetrahedron
w, (19831, 24, 5181
SECTION 167
K E T O N E S FROM A C I D S
1 . iPr2Zn, Et20, 0-23°C BnPdCl ( PPh3)2
nC3H7CC1
Grey, R.A.
0
2. 3 N H C 1 , 1 6 O C
PhCCl
0 II -n C 3 H7 C i P r
t
98%
J Org Chem, (19841, 49, 2288
CH3CH2CH21,
I1
207
Zn-Cu
Pd(PPh3)4 PhH -DM F
cat.
0 It
*
PhCCH2CH2CH3
*
Tamaru, Y.; Ochiai, H.; Sanda, F.; Yoshida, Z. Tetrahedron L e t t , (1 9851,
-
0
1 . C p 2 T i = C H 2 , -20
It
PhCH2CC1
2. H C 1 ( s ) ,
Stille, J . R . :
Grubbs, R.H.
- 1 0°C
*
-
3°C
26, 5529 0
>
I1
PhCH2CCH3
J: Am Chem Soc, (1983),
97%
9, 1664
n
3. a q . HC1
*
85%
Fujisawa, T. ; Mori, T.: Higuchi, K.; Sato, T. Chem Lett, (1983), 1791
--
I
77%
Me
208 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CU20/O2
*
Ph2CHCOOH CH3CN,
50"C,
PhCPh
15h
57%
Toussaint, 0 . ; Capdevielle, P.; Maumy, M. Tetrahedron E,(19841, C02SiMe3
1
CH2
I
C02S iMe3
Rathke, M.W.
CH20Ac
I
(CH2)4
I
c-c1
br
1 . MgC12, N E t 3 , E t 2 0 2 . PhCC1, O ' C , l h II 0 3.
* ; Nowak,
SECTION 167
5N HC1,
0
II
PhCCH
>
reflux
Syn
M.A.
25, 3819
90%
Camnun, (1985),
3,1039
1 . EBuMnI, E t 2 0 -50°C
-
RT
2 . a q . HC1 , 0°C
CH20Ac
i
*
( CI H 2 ) 4 0
2h
95%
Friour, G . : Cahiez, G.*; Normant, J . F .
E t 3 A 1 , THF,
Synthesis, (1985), 50
25°C
PhCCl
Wakamatsu, K . ; Okuda, Y.;
Oshima,
&""B" -
* K. ; Nozaki,
*
0
II
PhCEt 70%
H.
Bull Chem Soc *,(1 9851, 58, ---
2425
SECTION 168
0
K E T O N E S F R O M ALCOHOLS
1. nC7H15MgBr,
II
THF,
RT
N i ( d p p e ) C1
PhSCCl
2. IBuMgBr, THF,
209
*
Fe(acac)3 0°C
E C ~ H5 C~ ~ B u
84%
Cardellicchio, C.; Fiandanese, V.: Marchese, G.*: Ronzini, L. Tetrahedron Lett, ( 1 985), 26, 3595 SECTION 168: Ketones from Alcohols and Thiols \OH
1. Cr(C0)6 2. Ac20/Py
t 3 . CH-CHMeOTMS, L
Reetz, M.T.
ZnCl I2
,
4. * ; Sauerwald, M.
Q&OH
[
A
H+
22°C
67%
CH2C1
Tetrahedron E,(19831, 24, 2837
12Cr207
-2
bo
-
A
95% * Lopez, C.; Gonzalez, A.; Cossio, F.P.; Palomo, C. -Syn Conmun, (19851, 15, 1197
0 OH
CH2C1 2 - C C 1 2 CH3C03H,
* Corey, E.J. ; Barrette, E.P.;
4 y
0°C
30 min
*
Magriotis, P . A . Tetrahedron E,(1985),
96%
26, 5855
210 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 168
P
4 [ HN-NL J H]'CrO3C1 CH2C12, 7h Davis, H.B.:
Sheets, R.M.;
G.L.
*
82%
Brannfors, J.M.; Paudler, W.W.;
Card,
Heterocycles, ( 1983) , 20, 2029
BU
5% P d ( O A c ) 2 6% PPh3, NaH, T H F
P h B r , 50°C
Bu
*
80%
Tamaru, Y.: Yamada, Y.; Inoue, K . ; Yamamoto, Y.; Yoshida, Z. J Org Chem, (19831, 48, 1286 ---
b
Choudary,
Pd(OAc)2/NaHC03 PhI, Bu4NC1 , DMF RTj 48h
* B.M. ; Reddy,
-6 95%
N.P.; Kantam, M.L.: Jamil, Z. Tetrahedron L e t t , (19851, 26, 6257
-
OH (NH4)6M07024'2H20 I C H ~ C H ( C H ~ ) ~ C H ~ OTHH F , 7 d , R T 30% H 2 0 2 , K 2 C 0 3 Bu4NC1
*
*
Trost, B.M. ; Masuyama, Y .
0
II CH3C(CH2)8CH20H
Tetrahedron L e t t , (19841,
7 9%
3,173
SECTION 168
KETONES FROM ALCOHOLS
Et H OCH 2 C H C H ~ P ~
3 LBuOOH, PhH
I
OH
21 1
E t
*
8 O o C , 24h
HOCH2bHCnPr II0
97% Kaneda, K.; Kawanishi, Y.; Jitsukawa, K.; Teranishi, S. Tetrahedron Lett, ( 1 9831, 24, 5009 Mo(CO)~, cetylPy.HC1 MgS04, 4 h 96%
* : Ogawa, M.
Yamawaki, K.; Yoshida, T.; Suda, T.; Ishii, Y. Synthesis, ( 1986 1 , 59 P M O 2~ 0 4 0 ~ - 3 c e t y l p y 3
7 85 hO C
quant. * * Yamawaki, K.; Yoshida, T.: Nishihara, H.; Ishii, Y. : Ogawa, M. -Syn Cornnun, (1986), 16, 537
6
NaBr02, a q . AcOH RT,
Kageyama, T.;
* Ueno, Y. ; Okawara, M.
OH
AcOH, C O ( O A C ) ~
1
CH3(CH2)4CHCH3
8
-t
30 m i n
84%
Synthesis, (1983), 815 0
li
*
CH3(CH2)4CCH3 67% * Morirnoto, T. ; Hirano, M.; Wachi, M.; Murakami, T. --JCS Perkin 11, (19831, 1949 N a B r , 60°C, l h
BaMn04, PhH r e f l u x , 15h
&OH
*
Firouzabadi, H. ; Mostafavipoor, Z.
*
$0
90%
Bull Chem Soc Jpn, (19831, 56, 914 ----
212 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
OH
I
CH2=CHCHCH3
5% t r a n s Mo ( N 2 ) ( d p e l
SECTION 168
0
II
CH3CCH2CH3
-P
PhH, reflux, l h
95%
Tatsumi, T.: Hashimoto, K.: Tominaga, H.; Mizuta, Y.; Hata, K . ; Hidai, M.: Uchida, Y. -J Organomet Chem, ( 1 9831, 252, 105
-
1 . BF3*OEt2, DCC
CH,Cl,,
RT, lh
2. P h I O , 0 ° C - R T 4h ~~
0
II
7
PhC( CH2)3CH=CH2 81 %
*
Ochiai, M.; Ukita, T.; Nagao, Y.: Fujita, E. JCS Chem Cam, ( 1 9841, 1007
---
0
II
1 . C1 C O C H 2 C H = C H 2 2 . Pd(OAc)2,
8 0 " C , 2h
Tsuji,
OH
I
* J. ; Minami,
PhCHCH3
CH3CN
t
I.; Shimizu, I. Tetrahedron Lett, ( 1 9841,
-
Pt-Ti02, PhH hv,
15h
*
t
7 6%
25, 2791 PhCCH3 83%
Kussein, F.H.; Pattenden, G. ; Rudham, R.: Russell, J.J. Tetrahedron Lett, ( 1 9841, 25, 3363
-
SECTION 168
+
OH
I
F R O M ALCOHOLS
KETONES
-
B nNMe O M o B r
t B u O O H , THF
CH3( C H 2 ) 6 C H ( CH2)30H
21 3
60"C,
C H 3 (CH2) gC(CH2)30H
24h
* Masuyama, Y. ; Takahashi, M.;
0
II
60%
Kurusu, Y. Tetrahedron Lett, ( 1 9841,
c e t y l NMe3 CH2C12,
-
t
Mn04
25, 441 7
-
30°C
1 .5h
OH
*
90%
Rathore, R.; Bhushan, V.; Chandrasekaran, S. -Chem Lett, (19841, 2131
OH
I
C H 3 (CH ) 5 C H C H
0 RuC13(H20),/NaBr03 A1 i q u a t 3 3 6 ,
C H C l 3/HOH,
RT
*
I1
CH3(CH2)5CCH3 82%
4.5h
*
*
Yamamoto, Y.; Suzuki, H. ; Moro-Oka, Y. Tetrahedron Lett, (1 9851,
26,
OH
I
PhCHPh
21 07 0
3 Ag2Fe04, reflux,
PhH
0.8h
>
I1
PhCPh 97%
Firouzabadi, H.: Mohajer, D.; Moghaddam, M.E. Syn Coamun, (1986), 16, 211
21 4 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 168
0
OH
I
Kanemoto, S.; Tomioka, H.;
I1
*
CAN
CH3 ( CH2)7CHnPr
CH3(CH2)7Cn-Pr
* Oshima, K. ; Nozaki, H.
Bull Chem Soc Jpn, ----
(19861,
9 4%
2, 105
Ba F e 0 4 PhH,
reflux 24h
*
80%
Firouzabadi, H. ; Mohajer, D.; Enterzari-Moghaddam, M.
-Syn C m u n ,
OH
PhH,
I
C H ~ C (HC H ~5 ) ~
~
Ni(R),
( 1 9861,
reflux
3 Dean S t a r k t r a p
*
3h
*
Krafft, M.E. ; Zorc, B.
16,723
J Org Chem, (19861,
CH3C(CH2)5CH3 93%
2, 5482
Review: ?Thromiun ( V I ) Based Oxidants”
*
Firouzabadi, H. ; IranpOor, N.; Kiaeezadeh, F.: Toofan, J. Tetrahedron, (1986), 3, 719 Related Methods: Aldehydes from Alcohols and Phenols (Section 481
SECTION 169
KETOP!ES FROM ALDEHYDES
SIXTION 169: Ketones
CHO
I
Ph-C-CH2CH=CH2
from Aldehydes
[ R h ( c h ir a p h o s ) 2 ] C 1
I
; Young, C.G.
JCS Chem Corrm, ---
1 . C 1 C 0 2 E t , NaCN, R T Bu4NC1, C H 2 C 1 CHO c 2 . NaH/DME, c l a l
RT, 1 .5h 3 . M e I , 0°C - RT
* Au, A.T.
Q
Syn Corrmun, --
(19841,
2,743,
*
749
0
Q
P P h
I
*
Ph
2 . KOH/MeOH
Anders, E. ; Gassner, T.
76%
Chem Ber, --
1 . EBuMgBr, VC13 CH2C1 2 , PhCH3
*
\
50%
I1
QJCHO
c'K 0
1 . PhCOC=PPh3
*
Cfh
(19831, 1215
0
CHO
50%
(52% ee S ) 3S-bis-(diphenylphosphino) butane
i
James, B.R.
*
160°C, 10h
CH3 c h i r a p h o s = 2S,
21 5
2 . CH2C12, r e f l u x
Hirao, T. ; Misu, D.: Agawa, T.
J Am Chem ----
(1984),
117,1034
*
Soc, (19851,
66%
107, 7179
0
216 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 /
V
NO
N
y NH' 0
CH3CH0
M~o-K+,K ~ C O ~
*
SECTION 170
* 72%
Kirmse, W. ; Hellwig, G.; Van Chiem, P.
Chem Ber, (1986), --
119, 1511
-
SECTION 170: Ketones fran Alkyls, Methylenes, and Aryls
This section lists examples of the reaction R-CH,-R' R-c ( =o)-R'
3 . CH2CHkC1,
Q
3
Beswick, P . J . ;
0
Muzart , J.
0
THF, 2 h -78°C- RT
3
62%
Leach, S.J.; Masters, N.F.; Widdowson, D.A. JCS Chem Coam, (19841, 46
---
RuC13,
NaI04, 21h
CH3CN,
RT,
CH2Cl 2/CC1
*
pH 7
Hasegawa, T.; Niwa, H.; Yamada, K.*
PhCH2Ph
+
62% P O Chem Lett, (19851, 1385 *
*
, O O C , 8h
0
II
I1
PhCPh 87% (46% conversion) Tetrahedron Lett, ( 1 986), 27, 31 39
-
-
SECTION 172
KETONES FROM A Y I N E S
21 7
SEXTION 171: Ketones from Amides
-
--
Me
Comins, D.L.
* ; Brown,
8 5%
J.D.
Tetrahedron Lett, (19831, 2, 5465 0
1 . P h L i , THF, O ° C
*
lh
2 . H30
t
I1
PhCCH3 77%
Wattanasin, S . ; Kathawala, F.G. Tetrahedron Lett, (1984), 25, 811
-
SECTION 172: Ketones -from Amines
6
1 . C1C02Me 2 . MeOH, E t 4 N O T s , e 3 . MeOH, 5 % H2S04
Me0 OMe
* 69%
*
Shono, T. ; Matsumura, Y.; Kashimura, S. -J Org Chem, (1983), 18, 3338
218 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 173
SECTION 173: Ketones from Esters
0
II
0
nBu2CuLi, E t 2 0
CH3(CH2)6CSeMe
-78OC,
w
I1
CH3(CH2)6C~Bu
15 min
96%
Sviridov, A.F.: Ermolenko, M.S.: Yashunsky, D.V.; Kochetkov, N.K. Tetrahedron E ,(19831, -n ritlu - 2
* Kim, S.
Lee, J . I .
c
LUL ’ ’i ,
(1983), 48, 2608
I1
d
1 . LiCH(rJC5Hl,)P(OEt)2 RT
3. (COC1)2, DMSO,
NEt3
CH2C1 2 , -6OOC 4 . !aH,
THF,
* &
“CgH1
-78OC
2 . NH4C1, H O H ,
I!
nBuC( C H 2 ) 5 B r
90%
0
THF,
4355, 4359 0
Et20 t
JOrg Chm,
24,
1
27%
RT
Attenbach, H.-J. ; Holzapfel, W.; Smeret, C.: Finkler, S.H.
26, 6329
Tetrahedron Lett , (1 9851,
P hC O-N=C
fH3 1 . CH3CH2CHMgBr
QN
\
C H 2 C 12 ’ T H F y Ph
2 . HOH
* Miyasaka, T. ; Monobe, H.:
Noguchi, S.
0 OoC
I1
PhCyHCH2CH3 CH3 72%
-Chem Lett,
(19861, 449
21 9
KETONES FROM ETHERS
SECTION 174
0
1 . Me3SnCH2-,
I1 PhCOCH2CH3
-78OC,
0
THF
It
3h
PhCCH3
-t
2 . a q . NH4C1
*
Sato, T. ; Matsuoka, H.;
84% Igarashi, T.: Murayarna, E. Tetrahedron L e t t , (1986), 3, 4339
-
SECTION 174: Ketones -from Ethers, Epoxides, and Thioethers
-
0
CH3
I
/ \
Me2C-CH(CH2)2fH Bn0CH2CH2
5% L i c 1 0 4 ,
CH2C1 2 / T H F ,
OSiMe3
I
I1
Me2CHC(CH ) CH
91 %
2l
*
B nOCH 2 C H
K.; Torii, S. Tetrahedron Lett, ( 1 9831, Fujii,
Cr03,
PhCHPh
RT
P t e l ec t r o d e s
Uneyama, K.: Isimura, A.;
0
e-
H2S04
acetone
2,2857 0
II
t
PhCPh
82%
*
Baker, R . ; Rao, V.B. ; Ravenscroft, P.D.; Swain, C . J . Synthesis, (19831, 572
0
II S-C H C P h I
1.
hw,
PhH
2 . MeO-N-OSiMe2tBu
*
II
CHMe
3 . TBAF,
Vedejs,
* E. ; Perry,
D.A.
THF
J Org Chem, ---
86%
(1984),
2, 573
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
220
0
Bn
3 NaSePh
0
"
PhS,
/ \
/
C-CHMe
RT,
SECTION 175
t
20 m i n
92% Izawa, T.; Sakata, K.;
Satoh, T . ; Kpeko, Y.; Yamakawa, K .
Kumagawa, T.;
Satoh, T.: Kaneko, Y . ;
Izawa, T.; Sakata, K . ; Yamakawa, K. --wlll Chem SocJp~,(1985), 58, 1983
0
/ \
nC8H1 , C H - C H 2
Chem Lett, --
(1984), 1957
0
S m I O , THF RT,
I1
*
20h
nC8H, 7 C C H 3 85%
SmIO = 2 S m 1 2 t 1 / 2 O 2
Prandi, J.: Namy, J.L.:
*
*
Menoret, G.; Kagan, H.B. J Organmet Chem, (19851, -
285,
449
SECTION 175: Ketones from Halides and Sulfonates
-
PhI, CO, CH3CH2CH21
Tarnaru, Y.;
Zn-Cu,
-
0
Pd(PPh3)4
THF,
50°C,
I1
Id)
PhCCH 2 C H 2 C H
(75% conversion) Ochiai, H . ; Yamada, Y.: Yoshida, Z.
-
*
90%
Tetrahedron Lett, (19831, 24, 3869
1 . Mg,
3. EtfiI20,
0
Friour, G.; Alexakis, A.:
0
THF
II
THF:PhH
*
82% t
Cahiez, G. ; Normant, J . Tetrahedron, ( 1 984), 40, 683
SECTION 175
AgOCCF3, 60°C,
* Ishihara, T. ; Kudaka,
PhCH2Br Tanguay,
221
KETONES FROM H A L I D E S
T.;
MeOH
20h
6 6%
T.
Ando,
Tetrahedron Lett, (19841,
Fe(C0I5,
2OoC
Ca(OHI2,
HOH
*
0
I1
BnCBn
+
BnCOOH
78%
CH2C12, 3h G.; Weinberger,
22%
* B . ; Des A b b a y e s , H . Tetrahedron Lett, (1 984), 3,5529
0 I
Ph3A1,
DMSO,
1 % PdC12(MeCN)2,
GPh
>
4OoC 4h
\
OMe
OMe
Bumagin, N.A.;
* I.P.
Ponomaryov, A.B.; Beletskaya, Tetrahedron Lett, (19851,
-
1 . Mg,
EteO
2. VC13,
nBuBr
Hirao,
25, 4765
-78OC,
* T. ; Misu,
3.
&I
CH2C12 20 min
,
-78x-RT
D.; Yao, K.; Agawa, T.
-
98%
2,4819
Meo
Tetrahedron Lett, (1986),
86%
3, 929
222 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 176
C O ~ ( C O ) ~M , e1 a q . NaOH, CO,
*
20°C,
PhH 20h
Me3Ncetyl Br
Miura, M. ; Akase, F.; Nomura, M. 1. Ac20,
DMF,
e-,
JCS Chem Ccm, (1986), 241 Mg a n o d e
s t . steel cathode
PhCH2C1
2.
Bu4NI, 10°C aq. H2S04
d'Incan, E.: Sibille, S.;
2 0%
54%
Perichon, J. Tetrahedron=,
0
It
PhCH2CCH3
80%
(19861,3, 4175
Related Methods: Ketones from Ketones (Section 177) Aldehydes from halides (Section 55) SECTION 176: Ketones from Hydrides
This section lists examples of the replacement of hydrogen by ketonic groups, RH + RCOR'. For the oxidation of methylenes, R,CO, see section 170 (Ketones from Alkyls and R,CH, Methylenes). -+
Bestmann, H.J
.* ; Schobert, R .
2,791
Angew Chan Int Ed Engl, (19851,
K E T O N E S FROM KETONES
SECTION 177
223
Ketones
SECTION 177: Ketones
This section contains alkylations of ketones and protected ketones, ketone transpositions and annelations, ring expansions and ring openings, and dimerizations. Conjugate reductions and Michael alkylations of enones are listed in Section 74 (Alkyls from Olefins. For the preparation of enamines or imines from ketones see
Section 356 (Amine - Olefin).
Me
65OC
63%
*
Shimizu, I.; Ohashi, Y.; Tsuji, J. Tetrahedron Lett, (1 9831, 2, 3865 CO,Et
1 . TiC13,
DME,
2. NEt3, 3. DME,
*
-
LiA1H4 10 min reflux,
reflux,
1 .5h 24h
4 . a q . MeOH
McMurry, J.E. ; Miller, D.D.
Go
M e A l C1
82%
J Am Chem Soc, (19831, 105, 1660
t
CH2C12 25OC,
0
3h
(9
')
85%
Snider, B.B.** Cartaya-Marin, C.P. J Org C h m , (19841, 49, 153 J Am Chm-SGE (19831, 105,2764 Snider, B.B.*i Kirk, T.C. ----
224 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . IBuMgBr,
0
II
2.
CICH~CCH~C1
-20
-
Li,
-20
SECTION 177
MgBr2
2OoC,
-
4.5h
0
*
2 0 0 ~
II
CH3CH2CcBu
3 . a q . HC1
Barluenga,
180°C, 2h * J. ; Florez, J.: Yus,
2 5%
4.
* ; Hahn,
Molander, G.A.
0
II
PhCCH2Br
quant,
J Org Chem, (1986),
G.
1. LiN(TMS)2,
2.
TMS-C1,
THF,
-78OC
3. 2 CBuLi, 4. aq.
Synthesis, (1983), 647
M.
-
-78OC RT
-78OC
PhCCH2CH3
II
t
PhCCH2SiMe3 51 %
*
Wierner, D.F. -J Org Chem, (19861,
II
0
NH4C1
Sampson, P.; Hammond, G.B.;
0
51, 1135
51, 4342
1 . K H , THF, t B u M e 2 S i C 1 / N E t 3 2 . t B u L i - T M E D A , nC6H14,
-1
ooc
3. ~ B u 1 ,-5"C,
45 m i n
*
0
II
P h C C H C H 2nBu
4 . HOH
*
62%
Trirnitsis. G. : Beers, S.: High, J.: B r u t t s , D.
Ridella, J.; Carlon, M.;
--JCS Chem Carm, (1984),
Cullin, D . ;
1088
SECTION 177
KETONES F R O M KETONES
225
-6 0
0
0
I
1'
CH3CCH2
NH3,
Galli, C.: Bunnett, J . F .
-
, FeS04
DMSO,
*
1 0 min
60%
J Org Chm, (19841,
d
*
P h C H 3 , Mn(OAc)7 AcOH, r e f l u x
CH3CCH3
3,3041
51%
CH,
( 2 : m : ~= 6 8 : 2 0 : 1 2 )
Cardrat, C.
Bull Chem Soc Belg, (1984),
NMe2
II CH3CH2CH2CCH2CH3
Fe(N0)3 C H 2 C 1 2, r e f 1 u x
78 %
*
Ph'fi'p,
0 II CH3CH2CH2CCH2CH3
K-10 c l a y
Laszlo, P. ; Polla, E.
n
93, 897
Tetrahedron Lett, (19841,
K-10 c l a y , F e ( N 0 ) 3
CH2C12,
2.5h,
RT
*
3, 3309
Ph
98 %
Balogh, M . ; Cornelis, A,*;
Laszlo, P.
#
Tetrahedron=,
(1984),
25, 3313
226 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
* Olah, G.A. ; Arvanaghi, M.;
SECTION 177
88%
Ohannesian, L.; Prakash, G.K.S.
Synthesis, (1 9841, 785
S
II
nBu4N
PhCPh
t
HS04-, C H 2 C 1 2
3N NaOH, R T , l h
0
I1
w
PhCPh 90%
Alper, H.: Kwiatkowska, C.; Petrignani, J . - F . ; Sibtain, F. Tetrahedron Lett, (1986), 7, 5449 K-10 c l a y , C H 2 C 1 2
S
Ph!QN02
0
*
Ph1'oN02
F e ( N 0 3 ) 3 , R T , 30 min
94%
Chalais, S.:
* Cornelis, A.; Laszlo, P. ; Mathy, A . Tetrahedron Lett, (19851, 26, 2327
0
II
CH 3CCH 2 C O O H
Kjonaas, R.A.*;
0
1 . C B u L i , T H F , 0°C 2 . B n B r , T H F , 3d O°C - R T
Patel, D.D.
w
II
CH3CCH2CH2Ph 92%
-
-
Tetrahedron Lett, (1984), 25, 5467
SECTION 177
b
2 27
KETONES FROM KETONES
DMF, N E t 3
1 . Me3SiC1,
reflux, 17h 2 . EtC(Me)2C1 , TiC14 C H 2 C I 2 , -5"C, 2 . 5 h
* 38%
Reetz, M.T.*; Chatzoosifidis, I.: Hubner, F.; Heimbach, H. OrgSlm_, (1984), 62, 95 /X
Q
K-10 c l a y , F e ( N 0 3 ) 3 CH.2C1 2
0 I1 X = NHCNH2,
7 0- 90%
N H S 0 2 T o l , NhPh
*
Laszlo, P. ; Polla, E.
q
Fe\+''
Ph,P
/
Synthesis, (1985), 439
1 . "BuLi,
.co
)f 0
-Q
-7SOC
2 . TFlSCl 3. n B u L i , THF, - 7 8 ° C 4 . CH20, THF 5 . MeLi, - 7 8 ° C
w
6 . Me1
Davies, S.C. 0
77%
* : Walker, J.C.
--JCS Chem C m
, (19851, 209
0 I1 THF, - 6 3 ° C Cp ( C 0 ) 2 F e C C H 3 + Cp ( C O ) 2 FeCCH2CH2CH=CH2 2 . CH2=CHCH2Br 54% -63 - -20°C Tetrahedron Lett, (1985), 2845 Brinkman, K.; Helquist, P.
II
1 . LiN(TMS)2
*
26,
228 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 177
0 It
0
II
Me2CHCCHN2
1 . PhH, R h ( O C C F 3 ) 2 RT, l h 2.
CF3COOH, 2h,
CH2C12
0
It
*
Me2CHCCH2 P h
RT
86%
McKervey., M . A . * ; Russell, D.N.: Twohig, M.F. JCS Chem Conm, ---
4
(1985), 491
bPh
AcO
P h B r , cBu3SnOMe,
0
PdC12fP \ Me0
/
100°C
3 ) 2 3 PhCH3 5h
*
54%
)t
Kosugi, M.; Hagiwara, I.; Sumiya, T.; Migita, T.
--Bull Chem Soc *,( 1 9841, 57, 242
0 11
f(CH2)5CH3 FH2 COCH2CH=CH2
I/
Pd(OAc)2,
PPh3
dioxane,
r e f 1 ux
NH40CH0,
35 m i n
* Tsuji, J. ; Nisar, M.;
0
Shimizu, I.
--J Org
1 . CH3MgBr, -70°C, NO 2
2.
*
DDQ,
Chem, (1985),
0
11
CH3(CH2)5CCH3 99%
50,
341 6
THF
10 min O°C,
3h
Bartoli, G. ; BOSCO, M.; Dalpozzo, R. Tetrahedron Lett, (1985),
n02 80%
26, 115
K E T O N E S FROM KET0NE.S
SECTION 177
n-
PhCCH2SiMe3 Fiorenza,
A.
0
BnBr, C s F
It
I1
*
RT, THF, 1 2 h
* M. ; Mordini,
229
PhCCH2CH 2P h
7 0% A.: Papaleo, S.: Pastorelli, S.; Ricci,
-
Tetrahedron L e t t , (19851,
1 . E B u L i , -5°C 2. E C ~ H , ~ I ,R T 3 . C B u L i , -5°C
CH3CCH3
4. B n B r , R T 5. a q . H C 1
*
CH3(CH2)5CCH2Bn
*
94%
--- a,(1985), 2,407
Yarnashita, M. ; Matsumiya, K.: Tanabe, M.: Bull Chem Soc
nBu3SnH, PhH AIBN Ii I(CH~)~CCH=CH~ reflux, 3h 0
Porter,
* N . A . ; Magnin,
0
II PhCCHPh
1.
Leone-Bay, A.
*
*
Suemitsu, R.
+ oI1
I(CH2)6CCH
Ph2PLi, THF
J Org Chem, (19861,
CH
21CH2)7 H C = C H C? 22%
D.R.; Wright, B.T. J Am Chem Soc, (1986), ----
2. A c O H , M e 1
I
OH
26, 787
108,2787 0
t
2,2378
II
PhCCH 2Ph 76%
SECTION 177
230 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SeMe
I
K-10 c l a y , F e ( N 0 3 ) 3
n C 6 H , 3-C-SeMe 1 Me
pentane, RT, 90 m i n
* Laszlo, P. ; Pennetreau, P.;
*
nC6H,3CCH3 90%
Krief, A.
-
Tetrahednxl Lett, (1986),
C H =C,I0s iMe3
1 . Py, C I O '~C , N 3~. 5 h+ B F ~ 2. aq. H
Ph
w
t
Sakakura, T.; Hara, M.; Tanaka, M.
2,3153
gPh \
73% CI
*
JCS Chem Cum, ---
(1985), 1545
Reviews: tfHmenol ate Aniens" Werstiuk, N.H.
*
Tetrahedmn, (19831,3,205
"1 ,2-Carbonyl Transpositions"
Kane, V.V.
* : Singh, V.;
Martin, A.; Doyle, D.L. Tetrahedron, (1983), 3,345
flAlkylationof Ketones and Aldehydes via Nitrogen Derivativesfl Whitesell, J.K.; Whitesell, M.A.
Synthesis, (1983 , 517
ffReactiveEnolates from Enol Silyl Ethers" Kuwajima, I.; Nakamura, E.
Accts Chem Res,
18, 181 (1985) -
Ketones may also be alkyated or homologated via olefinic ketones (Section 374). Related Methods: Aldehydes from Aldehydes (Section 49)
SECTION 179
SECTION
KETONES FROM OLEFINS
178: Ketones
Nitriles
1 . L D A , T H F , -78°C 2 . 0 2 , - 7 8 " C , 30 m i n
3. S n C 1 2 , a q . H C 1 , 0°C 4 . 1 M NaOH
CN
QPh
Freerksen,,R.W.; Watt, D.s.~
t
Selikson, S.J.; Wroble, R.R.: J Org Chem, (19831,
c
Ph
DMSO,
65%
Kyler, K.S.;
48,
*
Kulp, S.S. ; McGee, M . J .
nPrCH'
OH
1
n Pr CH CH *CH 2CN
*
J Org
2.
/o"" \
93%
Chem, (19831,
80% a q . A c O H lh
J Org
179: Ketones
Set, L.
Chem, (1984),
g , 4097
66%
$9, 1313
Olefins
0
0 2 , PdC12, 8 O o C
CH3(CH2)7CH=CH2
Br
Ph
1 . PhH, Ph3SnH, 15h AIBN, reflux
Clive, D.L.J. ; Beaulieu, P.L.: SECTION
4087
t
02, HOH
K2C03, o v e r n i g h t
Br
-
231
CuC12*2H209 PhH Et3Ncetyl B r , H O H
J a n u s k i e w i c z , K.; A l p e r , H.
~
*
-
II CH~(CH~)~CCH~
-
73%
Tetrahedm Lett, (19831, 24, 5159
232 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
n
SECTION 179 n
1 0 atm CO c o ,L (. C O ) 1 0 atm H 2 , 20h n ,
I
1 2OoC, h e x a n e 7 6%
Eilbracht, P.x: Acker, M.; Totzauer, W. Y
*
-Chem Ber,
(19831,
Eilbracht, P. ; Balss, E.: Acker, M.
nC8H, 7 C H = C H 2
116,238
25, 1131
Tetrahedron Lett, ( 1 9841,
1 . PdCl L" , CuCl , RT 02,DMF:H20, 24h
0
I1 n C 8 H 1 7CCH3
-
2 . 3N HC1
c
Tsuji, J . ; Nagashima, H.: /
ZrCp2
* Nemoto, H.
73%
Org Syn, (19841,
62,
1 . 3 CH C H 2 C H 2 C H = C H 2 3 P h H , 3OoC, 2h 2 . C O Y -78OC, 3 . AcOH
6h
68%
Yasuda, H.; Nagasuna, K.; Akita, M.; Lee, K.; Nakamura, A. Organmetallics, ( 1 984 1, 3, 1 470 1 . NaBH30Ac, T H F , 50°C 2 . NaOMe, CHC13, 5OoC
*
-,,,
3 . H 2 0 2 , NaOH
Narayana, C.; Periasamy, M.
*
-
5 9%
Tetrahedron Lett, ( 1 9851,
26, 6361
Review: llSyntheticApplications of the Palladium Catalyzed
Oxidation of Olefins to Ketones"
*
Tsuji, J.
9
Synthesis, (19841, 369
SECTION 180
233
KETONES FROM M I S C .
See also: Ethers and Epoxides from Olefins (Section 134) and Ketones from Ethers and Epoxides (Section 174). SECTION 180: Ketones from Miscellaneous Compounds
Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from Olefins). 0
/CH 3
Ni(R),
PhCH=C
aq.
\
N02
EtOH,
pH 5
It
*
NaH2P02.xH20
PhCH 2 C C H
40-60°C
2h,
88%
*
Monti, D. ; Gramatica, P.; Speranza, G.: Manitto, P. Tetrahedron Lett, (19831,2,417 1 . e-, fH3 nC6H13CH=C -
a q . HC104
\
2.
* : Tanaka, H.;
Katoh, T.
1 . LiBH=Bu3, THF,
Mourad, M.S.: Varma, R.S.:
81 %
-Chem Lett,
(19831, 607
THF
RT
4N H 2 S 0 4 ,
_?C6H1 3 C H 2 C C H 3
>
3% a q . HCHO
Torii, S.
2.
0 II
Pb e l e c t r o d e s CH2C1 2 / d i o x a n e
-10°C
>
* Kabalka, G.W.
Synthesis, (1 985>, 654
81 %
234 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . F B u L i , OOC, l h 2 . B n B r , - 7 8 - 20°C, 2 d
N=CHEt
I
HN I CMe3
3. T F A , 2 O o C , 6 h
4. (COOH)2,
aq.
*
SECTION 180
0
II CH3CH2CBn
*
Et20, 14h
67%
Adlington, R.M.; Baldwin, J.E. ; Bottaro, J.C.; Perry, M . w . D . JCS Chem Comn, (19831, 1040 ---
1 . LDA, THF MMe 2 . nC H CH,B,y 6 13
CN I PhCHNM e 2
0 I1 ,llCgH1 3 PhCCH.
HMPT
b
\ 3. a q . H 2 S 0 4 70% CH3 4. A g N 0 3 ( 7' 6 % Hebert , E.*; Maigrot, N.; Welvart, Z. Tetrahedron Lett, ( 1 I
(S)
N-~Bu II Me2N-C-NMe
NO,
COOH
CH,C1 ,, RT * L L Barton, D.H.R. ; Motherwell, W.B.: Zard, S.Z.
-
Tetrahedron Lett, (1983),
CH3(CH
) CH N O
1. nBuLi, THF -90 - - 3 o o c
*
0
95%
2, 5227
;-OH CH3(CH2)4CCH2Bn
2.C1HC=NMe2'C13. B n C H 2 M g B r , C u I 97% THF, -3OoC, 2 h * Fujisawa, T. ; Kurita, Y.; Sato, T. -Chem Lett, (19831, 1537
SECTION 180
KETONES FROM MISC.
acetone,
5
LBuOK
235
\
NO2
Iwasaki, G . : Saeki, S.; Hamana, M.
N02
HC02Na,
I
IC$-$5;H
e
CH C H C C H 3
211
Nokami,
8h
0
I1
*
I C ~ H ~5CFH2
T.:
CH 3 C
0
90%
Synthesis, ( 1983), 763
DMF,
0
KI
80"C,
CH3 (CH2
II
5 C ( CH2) 5 C H 3
2 . a q . HC1
Ryu, I . : Ryang, M.;
CH2
\\
20°C Wakabayashi, S.
1. Ni(C0)4, CH3(CH2)5HgBr
MeOH
Chem Lett, (1986), 31
P t electrodes
0
* J. ; Sonoda,
-,
*
59%
96%
*
Rhee, I . ; Omura, H.; Murai, S. ; Sonoaa, N .
Syn Carmun, (19841,
2, 1175
Na2Sn02 15 min
Varma, R.S.; Varma, M . ;
*
* Tetrahedron Lett,
Kabalka, C.W.
6" 86%
(19851,
26, 6014
236 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 180A
Ne,
N ,CC1 II0
1 . O RT, , N ~2 4Oh , H MeCN , K ~ C O ~
I
2 . AgN03,
,CHC N
1 . "BuLi,
CHS02Ph
2.
THF,
TMS-OO-TMS,
NO2
78%
Tetrahedron=,
E t
I
nC5H,
\
30 min
Kay, I.T.; Glue, S.E.J.
;"
*
THF
aq.
(1986),
2,113
-78OC -78OC-RT
nC5H, C E t
overnight 3 . a q . NaHCO
Hwu,
* --J.R. J Org Chem,
7 6%
-
(19831, 48, 4432
SECTION 18OA: Protection of Ketones
-
See Section 362 (Ester-Olefin) for the formation of enol ethers and Section 367 (Ether-Olefins) f o r the formation of enol ethers. May of the methods in Section 60A (Protection of Aldehydes) are also applicable to ketones.
A
a
5- , -:
-
1 . 2 HSCH2CH2SH
-
ZnOTf,
OSiPh2tBu2.
reflux,
2h
bqh *
THF/hexane
ZnBr2,
3. BnBr,
Saigo, K. ; Kasahara,
85%
2, 169
Tetrahedron Lett, (1983),
1 . LDA,
4 . H 0'
S QOSiPh2LBu
U
* Corey, E.J. : Shimoji, K. 2.
-t
23°C
0
OMe
0-
RT 0°C
-
reflux
*
i.; Ogawa, S.; Nohira, H.
bP 7 9%
(82% ee S )
-
Tetrahedron E ,(19831, 24, 511
SECTION 180A
PROTECTION
1
.
OF
KETONES
237
i B u 2 A l SCH2CH2SA1 i B u 2 PhH, R T , 3 0 m i n
2 . 3M HC1
e
3 . 1 0 % NaOH
Satoh, T.; Uwaya, S.; Yamakawa, K.
’0””’r
LiC104,
e-,
0 0
Q
Chem Lett, (1983), 667
y-y r
CH2C12
Pt electrodes
*
TMSOCH2CH20TMS
* Torii, S. ; Inokuchi, T. 0
*
91 %
Chem Lett, (19831, 1349
0
1 . HOCH2C(Me2)CH20H 0.4M
a q . H2S04
t 2. continuous e x t r a c t i o n Na2C03
Babler, J.H.*; Spina, K.P.
Syn Coamun, (15841,
TMSOCH2CH20TMS, 5h
85%
-78OC
*
2, 39
n
8
Sakurai, H.*; Sassaki, K . ; Hayashi, J.; Hosorni, A. J Org Chem, (1 984), 3, 2808 -
86%
238 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 180A
(EtO),Si(CH,),NH,.HCl
-*
Me0
MeOH, R T
3
Me0
97%
Misiti, D.; Palmieri, G. Tetrahedrm, (19841, 110, 1491
Gasparrini, F.: GiOVaMOli, M.: "NMe,
mc p b a
\\d'
Duraisarny, M.:
DMF, Walborsky, H.M.
-63OC quant.
*
--J Org Chem,
(1984),
Gravel, D.*:
Murray, S . : Ladouceur, G.
0
c e t y l NMe3 Mn04-
JCS Chem Comn, ---
*/o H
i-
CH2C12,
RT
2, 3410
90%
(1985), 1828
-8
Vankar, P.; Rathore, R.; Chandrasekaran, S. J Org Chem, ( 1 986), 51, 3063 PhI(OAc),, CH2C12 Moriarty, R.M.*; Prakash, 0. ; Vavilikolanu, P.R. Syn Commun, (19861, 16, 1247
-
98%
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 13 PREPARATION OF NITRILES
-
SECTION 181 : Nitriles
I
I
1 atm 5OoC,
Funabiki,
from Acetylenes
H,. HOH d .
i v 85%
10h
* T. ; Yamazaki,
-
I
Y.; Sato, Y.; Yoshida, S. (1983), 1915
JCS Perkin 11, ---
SECTION 182: N i t r i l e s from Acid Derivatives
--
No Additional Examples SECTION
183: Nitriles fran Alcohols -and Thiols No Additional Examples
-
SECTION 184: Nitriles from Aldehydes
-
CHO
1. NH20H-H20, 2.
CS2,
+
PhH,
B u 4 N tH S 0 4 - ,
NaOAc a q . NaOH
RT, 2 0 h
Shinozaki, H.*; Imaizumi, M.: Tajima, M. Chem Lett, (19831, 929
--
l I v 15%
240 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 OH
SECTION 184
6
0
Me2N C i - Z C l
M e 2 N a , CH2C12
CI
10 m i n
O O C ,
Arrieta, A . ;
* Palmo, C.
Synthesis, (19831, 472
0 11 Me3SiO(PO),, Ph-C-H
CI
, DCE
*
r e f l u x , 95 m i n
Aizpurua, J.M.: Palmo, C.
PhCN
92%
Nouv J Chem, (1983), 1,465
*
Nishiyama, K. ; Watanabe, A.
Chem Lett, (1984), 773
S8, NaN02, N H 3
PhCHO
95%
m
1 0 0 ° C , 4h
PhCN 74%
*
Sato, R. ; Itoh, Kao.; Itoh, Kaz.; Nishina, H.; Goto, T.; Saito,
M.
Chem Lett, --
(1984), 1913
SECTION 186
24 1
N I T R I L E S FROM A M I D E S
t
1 . C1 2C=NMe2 C1 DCE,
PhCH 2.
-
RT
-
refiux
e x c e s s PhNH2, RT
-
PhCN
t
DCE
95%
6OoC
3c
Kokel, B. ; Menichi, G.; Hubert-Habart, M. Synthesis, (1985), 201
E t N 0 2 , NaOAc AcOH,
G O M e
t
reflux
4h
*
Karmarkar, S.N.; Kelkar, S.L.; Wadia, M.S. Synthesis, ( 19851, 51 0 SECTION 185: Nitriles from Alkyls, Methylenes, and Aryls
--
No Additional Examples SECTION 186: Nitriles -from Amides 0
II
CH ( CH ) 4 C N H t B u
P0Cl3, reflux,
Perni, R.B.; Gribble, G.W.
PhH 6h
* Org-
*
CH3 ( C H 2 ) 4CN
97%
-Proc Int,
(19831,
15,297
242
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
:O2Et
CH 2 I NHCHO
1. P0Cl3, CH,Cl9,
iPr2NH
2. Na2C03,
HOH,
Obrecht, R.; Herrmnn, R.; Ugi,
S
2 BnCl,
II
?02et
0°C l h
SECTION 186
CH 1 2 NE C
RT
* I.
+
-
84%
Synthesis, (1985), 400
PhH
Bu4NBr
80%
*
Funakoshi, Y.; Takido, T. ; Itabashi, K. Syn Comnun, (19851, 0 --
9, 1299
I1
1. C13CCC1, NEt3 CH2C12, 5°C
0 I1 PhCNH2
* Saednya, A.
2 . HOH 3. NaOH 4. H2S04
t
90%
5 . HOH
Synthesis, (19851, 184
0 It
1 . C13CCC1,
0°C
-
PhCN
6°C
O2N
(MeO)3P
-
CN
2. ice/HOH
*
Mai, K. ; Patil, G.
93%
-
Tetrahedron Lett, (1986),
3, 2203
NITRILES FROM HALIDES
SECTION 190
243
SECTION 187: Nitriles -fran Amines
No Additional Examples SECTION 188: Nitriles -fran Esters
No Additional Examples SECTION 189: Nitriles -from Ethers, Epoxides,
Thioethers
No Additional Examples
-
SECTION 190: Nitriles fran Halides
Q I
Suzuki,
1 . NaCH(CN)C02Et, cu I
and Sulfonates ,CN
HMPA
2. a q . N a O H , 90°C
* H. ; Kobayashi,
T.; Yoshida, Y.: Osuka, Chem Lett, (19831, 193 --
HOH, H2, 55OC
* A.
-
24h
*
6 9%
64%
Funabiki, T. ; Nakamura, H.; Yoshida, S. -J Organomet
e, (19831,
3,95
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
244
nBu3SnCH2CN 1 2 O 0 C Y 3h
xyl ene
PdCl2[P-oTol3I2 Kosugi, M.;
I s h i g u r o , M.:
Sano, H.: Migita, T.
* : Farooq,
*A
CH2C12, r e f l u x 23h 0 . ; Surya Prakash,
78%
G.K.
Synthesis, ( 1 9851, 1 140 \CN
0
I
11
1 . NaCH(CN)P(OMe)2 17OOC - 2OOOC 2. a q . HC1
Suzuki,
*
(19841, 151 1
Me3SiCN, A1Br3
Olah, G.A.
Q
*
78%
Negishi, Y.;
Chem Lett, --
SECTION 191
* H. ; Watanabe,
K.:
Y i , Q.
* -Chem Lett,
59%
(1985), 1779
SECTION 191: Nitriles from Hydrides
1 . DMF, P0Cl3 OMe
2. NH40H-HC1
Liebscher, J.; Bechatein, U .
*
Zeit Chemie, (1983),
OMe
43%
23, 214
SECTION 193
245
N I T R I L E S FROM N I T R I L E S
SECTION 192: Nitriles f'ran Ketones
-
-
1 . SnC14,
EtS SEt V
U
2.
Me3SiC
Ni(R)
30% Reetz, M.T. * ; Muller-Starke, H. Tetrahedron Lett, (19841, 3, 3301
-
SECTION 193: Nitriles fran Nitriles
Conjugate reductions and Michael alkylations of olefinic n i t r i l e s ar e found i n Section 74D ( A l k y l s from Olefins). A1 203/KOH , E t B r Ph CH 2 C N
Sukata, K.
PhH,
*
40"C,
CN
I
*
4h
PhCHCH 2 C H 91 I
WiLl Chem Soc Jpn, (1983), 56, 3306
---K
+
-
Me2C-N02,
DMSO
*
1 .75h
Kornblum,
* N . ; Singh, 1.
74%
J Org Chem,
PhCH2C1, N i * ,
BrCH2CN
Ni
*
Boyd, S.D. (1984),
H.K.;
85"C, 2 . a q . HC1
30h
3, 358
glyme
*
= activated nickel
Inaba, S.; Rieke, R.D.
*
Synthesis, (19841, 842
P h CH 2 C H 2 C N
57%
246 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 195
1 . IBu3SnLi, -78OC
CN
HMPA,
I
Ph- C-SEt
2 . BnBr, THF,
I
CH 3
THF,
3. 1 N N a O H
*
Takeda, T. ; Ando, K . ;
30 m i n
-78°C
CN
-
I
Ph-C-CH2Ph
RT
I
CH 3
87%
Mamada, A.; Fujiwara, T. Chem Lett, (1985), 1149
--
SECTION 194: Nitriles fnw Olefins No A d d i t i o n a l Examples
SECTION 195: Nitriles from Miscellaneous Compounds
gJ-
Me3S i I , C H 2 C 1
NO*
Olah, G.A.
25"C,
* ; Narang, /
16h
t 98%
S.C.; F i e l d , L.D.; Fung, A.P. J Org Chem, (1983), 2766 ---
s,
1 . NaCN, 2.
25"C,
Pb(OAc)4 -2OoC,
-6
5 min
12h
88%
Masuda,
Y.;
Hoshi, M.;
*
Yamada, T.: Arase, A . JCS Chem Comn, (19841, 398
---
SECTION 195
N I T R I L E S FROM M I S C .
FVP 540°C,
N=C +
-
Meier, M.; Riichardt, C.
*
247
Torr) 25 m i n
97%
-
Tetrahedron Lett, (19841,
CN
25, 3441
T1 ( t f a ) ,
*
Taylor, E.C. ; Katz, A.H.: McKillop, A. Tetrahedron E ,(19841, NS i M e 3
II
P h C 0 s iMe
n~ u 4~ + F -
15"C,
20h
72%
3, 5473
m
PhCN quant.
*
Rigo, B. ; Lespagnol, C.: Pauly, M. Tetrahedron E ,(19861,
Murahashi, S.-I.
* : Naota, T.; Nakajima, N. J Org Chem, (19861, 51, ---
3,347
94%
898
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 14 PREPARATION OF OLEFINS
-
SECTION 196: Olefins from Acetylenes
-
1 . iBuMgBr
CH3(CH2)4CECSiMe3
*
CH 3 ( C H 2 ) 4
Cp2TiC1 2. CH2=CHCH2 CuI, CH21
e
\
/SiMe3
c=c,
FH
H’ 2 86% H2C=CHkHi
Sato, F. ; Watanabe, H.; Tanaka, Y.; Yamaji, T.; Sato, M. Tetrahedron Lett, (1983), 24, 1041
NaBH4-PdC1
P h - C=C
-Ph
Suzuki,
* N. : Tsukanaka,
PEG, CH2C12, PEG = p o l y e t h y l e n e g l y c o l
FeC12,
91 %
---
c,( C H S-S
*
P h CH = C H P h
T.: Nomoto, T.; Ayaguchi, Y.; Izawa, Y. JCS Chem Carm, (19831, 515
NaBH4, E t O H , Ph-Cs-Ph
*
30 m i n
Kijima, M.; Nambu, Y. ; Endo, T.
35OC, 8h
> )4hNH 0
*
7 5%
Chem L e t t , (19851, 1851
OLEFINS FROM ACETYLENES
SECTION 196
HCnC
Ph PhZnCl , T H F qH Et20 C02Me
Elsevier, C . J . :
*
3% Pd(PPh3)q
,\
= c\
Ph
80%
-
MeNH,.Ca c E D A , -25°C 4h
* ; Belmonte,
F.G.
*
L
quinol ine, H 2
Brunet, J.-J.; Caubere,
* P.
J Org ---
*
CH3(CH2)4CH=CHEt
--J Org Chem,
NaH/tAmOH/Pd(OAc), TH F/EtOH
P h C=C P h
H’
\c =
Stehouwer, P.M.: Westmijze, H.; Vermeer, P. J Org Chem, ( 1 9 8 3 , 48, 1103 ---
CH3(CH2)4CmCEt Benkeser, R.A.
Ph
249
79% (19841,
2, 1662
Ph
Ph
* 97%
Chem, (19841,
2, 4058
1 . Dibal-H, Et 0 -20°C - d f l u x 2 . M e L i , 0°C nC 6H 1 3 dS i M e 3 nC6H1 3 C E C S i M e 3 3 . C u I , P(0Et) THF, - 7 8 O ? t 4. E t I , -78°C - R T 5. ice/ d i l . HCI 78%
*
Ziegler, F.E. ; Mikami, K .
-
Tetrahedron Lett, (1984),
25, 131
250 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 196
- b P hMe2S i
PhMe2S iMgMe , Cu I HCEC ( C H
) 4~~~
THF,
0°C
-
25°C
91 %
Okuda, Y.; Morizawa, Y.: Oshima, K.*: Nozaki, H. Tetrahedron Lett, (1984), 25, 2483 1.
'
CH C Z C H E t OH
X'"
, THF-CH2C12 O"C,
2.
Me
5h
*
PhCH2CH2MgBr, C u I -3O"C,
3 0 rnin
\
C=C=CHE t
J
CH2CH2Ph 84%
* Fujisawa, T. ; Iida, S.; Sato, T.
Tetrahedron Lett, ( 1 984),
*
2.
PhH,
80"C, 4 8 h
25, 4007
95%
Wenkert, E. ; Leftin, M.H.; Michelotti, E.L. J Org Chem, (1985), 2,11 22 --SnMe3
2 Me3SnCu .SMe2 HC=C(CH~)~OH
*
-6O"C,
Piers, E. ; Chong, J.M.
THF/MeOH 12h
w
I
C H = C ( C H ) 4~~ 8 5%
JCS Chem C a m , (1983), 934
SECTION 197
251
O L E F I N S FROM A C I D S
PhMe2Si ZnE t 2 L i
t
CH3CrCCH20H CuCN,
25"C,
C H 3 C H = C H CH 2 0 H
THF
SiMe2Ph
Okuda, Y.; Wakamatsu, K.: Tuckmantel, W.: Oshima, H. Tetrahedron Lett, (1985),
-
,Ph
2% P d ( P P h 3 ) 4 , Sm12,
THF,
85%
* K . : Nozaki, 26,
4629
RT
2h 90%
Tabuchi, T. ; Inanaga, J.*; Yamaguchi , M . Tetrahedron Lett, (19861, 27, 5237
SECTION 197: Olefins -fran Acid Derivatives 1 . CH3CH2CH2MgBr, T H F -78°C - -60°C
0
Ii
CH3CHCC1
I
2. CH2=CHCH2MgBr,
c1
CH2CH2CH3
>
Et20
1
CH 3 C H = C C H = C H
3. L i , - 6 0 ° C - 2 0 ° C 87% * Barluenga, J. ; Yus, M . ; Concell6n, J.M.; Bernad, P. J Org Chm, (1983), 3,609 --+PPh3 I
+ C ;OOH
Et02CN.NC02Et
* (I:E =
i P r CH = C H P h 98:2)
73%
*
Mulzer, J . ; Lammer, 0.
Angew Chem Int Ed Engl, -----
(19831,
22,
628
252 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . CH2N2, 2 . HC1,
i PrCH2CC1
:
Barluenga, J.
Et20,
-20°C
Et20, overnight
E t I
0°C - RT iPrCH2C=CH2 3 . E t M g B r / M g B r 2 , THF 4 . L i , RT, o v e r n i g h t 75% Yus, M.; Concellon, J . M . : Bernad, P. J Org Chem, (19831, 48, 3116
-
P b ( OAc )4, C U ( O A C ) 2 * H 2 0
,,#+
OcooH DMF-AcOH,
SiMe,
Nishiyama, H.
SECTION 198
*
RT,
t
3h
72%
; Matsumoto, M . ; Arai, H.: Sakaguchi, H . ; Itoh, K . Tetrahedron Lett, (19861,
3, 1599
SECTION 198: Olefins from Alcohols and Thiols
-
-
--
CH3CN/Na I
0
Me3SiC1
Sarma, J . C . ;
@
HO
D'Onofrio, F.:
60%
10 min
OMe
Sarma, D.N.;
, RT
0 t
Sharm, R.P.
Barua, N.C.;
*
0
JCS Chem Conm, (1984) , 81 3 ---
l:sOH/SiO:h ref1 ux,
S c e t t r i , A.
*
~
@
17
97%
Synthesis, (19851, 1159
SECTION 199
O L E F I N S FROM ALDEHYDES
Fadel, A,; Salaun,
* J.
253
92%
Tetrahedron, (19851, 41, 1267 Tetrahedron, (19851, 3, 413
0
II
1 . C1P(OiPr)2, 2 . NaFp
Py
*
3 . HBF4
OH
4. NaI
Araki, S.;
Hatano, M.; Butsugan, J Org Chem, (19861,
---
1 . CH(OMe)3,
THF,
OHt i
0
2. sealed tube,
Ando, M.
24%
* Y.
* ; Ohhara,
140°C,
3
e
Ac20,
*
H.; Takase, K.
P 2h 3 PK 2 CC H0 32 P, r MeOH
1 .5h
90%
1.5h
Chem Lett, (19861, 879
t
25OC,
2126
12h
SECTION 199: Olefins from Aldehydes
b C H 0
51,
&
CH =CH P r
w
( & : I=
78%
82:18)
Le Bigot, Y.: Delmas, M.; Gaset, A. Tetrahedron Lett, (19831,
2,193
254 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 +-
SECTION 199
0 It
Ph3PCHCCH2CH2C02Me, D M F , 2 5 O o C , 22h Ronald, R.C.; Wheeler, C.J.
*
0 / '
2 C1Mo3c.i , T H F , -70°C 2
J Org Chem, ---
(19831, 48, 138
-
RT ____t Kauffmann, T.*: Fiegenbaum, P.; Wieschollek, R.
C H ~ ( C H ~5~~~ )
2. HOH
84%
(19841, 23, 531
Angew Chem Int Ed Engl, ----
1 . C13Mo=CH2, THF Et20, -70 - 20°C
70%
____t
t
CH3(CH2)5CH=CH2 6 5%
Kauffmann, T.; Enner, B.; Sandler, J.; Wieschollek, R.
----Angew Chem Int Ed -1,
(19831, 22, 244
1 . ( iPr0)3TiCH2CH=CHPPh2 - 7 8 O C - 0°C 2. M e I , 0°C
-
RT
(E:Z iFUkai, J.; Ikeda, Y.; Ikeda, N.; Yamamoto, H.
=
Tetrahedron Lett, (19831,
-
2 PhCHO
WC16' e - ,
t
4h
Petit, M.; Mortreux,
PhCHO
THF
A.;
Petit, F.
*
Clift, S.M.: Schwartz, J.
=
2, 4029 P h C H = C H Ph 88:9)
97%
* --JCS Chem Comn, (1984),
Cp2Zr(PPh3)=CHCH2tBu PhCH3, 3h
(r:I
4:96)
-t
341
PhCH =CH CH 2 t B u 7 6% (L:L = 1 :2)
J Am Chem Soc, ----
(1984), 106, 8300
SECTION 199
O L E F I N S FROM A L D E H Y D E S
CH212,
C H 3 ( CH ) 5CH 0
Zn, THF
20 m i n
RT,
*
255
C H ~ ( C H ~ ) ~ C H = C H ~
)%9)
71 %
Yamashita, J.*; Inoue, Y.;
Kondo, T . ; Hasimoto, H. Bull Chem Soc Jpn, (19841, ----
+
CH2=CHPPh3 Br-
1 . n-Bu2CuLi, THF HMPA, -5O"C, 9 h 2 . 5C5Hl1CHO
-
-20°C 3 . aq. NH4C1 -50
J u s t , C.:
tB
(Z:E - -
u
26,
1799
P hCH =CHtB u
(I:E =
* R.R,
58%
= 1:4)
*
25°C
2335
n B u C H 2 C H = C H n-C 5 H 1
Tetrahedron Lett, (19851,
O'Conno?, B.
PhCHO
t
57,
95%
1:4)
Freudenberger, J.H.; Shrock, Organometallics, (1986), 5, 398
@W I PhCHO
PhH,
25:C,
(OCH t B u ) 25 min
Aguero, A.; Kress, J.; Osborn, J . A .
t
D
C
HPh
88%
--JCS Chem Carm, (19861,
Related Methods: Olef i n s from Ketones (Section 207)
531
256 COMPENDIUM CF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 201
-
SECTION 200: Olefins -from Alkyls, Methylenes, and Aryls
This section contains dehydrogenations to form olefins and unsaturated ketones, esters, and amides. It also includes the conversion of aromatic rings to olefins. Reduction of aryls to dienes is found in Section 377 (Olefin-Olefin). Hydrogenation of aryls t o alkanes and dehydrogenations to form aryls are included in Section 74 (Alkyls, Methylenes, and Aryls from Olef ins). 7.
CH2=CHLBu
2.
(Me0)3P
95%
Baudry, D.* ; Ephritikhine, M.*: Baudry, D.*: EphritiWine*
I.
Felkin, H.; Zakrzewski, J. Tetr edron Lett, (19841, 25, 1283
e kin, H.; Holmes-Smith, R.
JCS C h a CODIII, (1983), 788
---
C H ~ N H ~D,E A ,
Ca
-25OC 2 . Et20, a q . N H 4 C 1
>
A+ 7 6%
* Benkeser, R.A. : Belmonte, F.G.; Kang, J. J Org Chem, (19831, 48, 2796 ---
'I!,
"+,
2 0%
SECTION 201 : Olefins -from Amides
No Additional Examples Related Methods: Alkyls and Aryls from Alkyls and Aryls (Section 65) Alkyls and Aryls from Olefins (Section 74)
SECTION 203
O L E F I N S FROM ESTERS
257
-
SECTION 202: Olefins -from Amines
No Additional Examples SECTION 203: Olefins -from Esters 1. nBuLi
II0 Ph2PCH2CH2iPr
2.
PhC02Et
3.
NaBH4,
EtOH
*
PhCH=CHCH2i P r
4 . N a H . DMF
49%
*
Buss, A.D.; Mason, R . ; Warren, S. Tetrahedron Lett, (1983),
2, 5293
1 . LDA "CgH17
CO2E t
2.
Ph2MeSiC1
3.
LiA1H4
___)
nC8H1 7CH=CH2
4 . B F 3 - O E t 2 , CH2C12
De Maldonado, V.C.; Larson, G.L.
32OoC,
*
Syn Caunun,
85%
(1983),
13,1163
sealed tube
1 .5h JPh OMe
OMe
Chwchaang, W.: Chantarasiri, N.; Chaona, S.; Thebtaranonth, C."; Thebtaranonth, Y. Tetrahedron, (19841, 40, 1727
55%
258 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . 2 MeMgI,
THF
reflux,
24h
/C02Et
2.
3 MeLi,
\
3.
9 ~ B ~ o - K + R, T
nC8H, ,CH -
S i Ph2Me
Hernindez, D.;
*
Larson, G.L.
reflux
SECTION 204
nC8H1 7CH=CMe2 54%
l h
J Org Chem, (19841,
s, 4285
1 . PhMe2Si)2CuLi 2 . LiA1H4
3. G N 0 2 SeCN,
CH3CH=CHC02Et
Bu3P
fH3 PhMe2S i C H CH=CH 50%
4. H202
*
Fleming, I . ; Waterson,
D.
1. 0'
P hCO 2 E t
*
2 . NaBH4,
--JCS Perkin \I CeC13,
I, (19841, 1809
, THF MeOH
-78°C 3.
>
PhCH =CH C H
(g
base
E l l i o t t , J . ; Warren,
* S.
96%
Tetrahedron Lett, (1986),
3, 645
SIXTION 204: Olefins from Ethers, Epoxides, p c J Thioethers S
I\
-?'12 H 2 5 C H C H 2
Schauder, J . R . :
P214,
DMF
8OoC,
12h
*
nC, 2 H 2 5 C H = C H 2
97%
*
Denis, J.N.; Krief, A. Tetrahedron Lett, (19831, 2, 1657
SECTION 204
45 rnin
reflux, Martin, M.G.:
Ganern, B.
*
80%
Tetrahedron Lett, (19841,25, 251
nBu3MnLi
&Ph \\\'
,+"
-
-30°C
Ph
* : Bisling,
Kauffrnann, T.
CH3 ( C H 2 ) 5CH-CH2
Barton, D.H.R.
0
nC5H1
/ \
66%
EtOH
ref1 u x
t
CH3( CH,),CH=CH2 92%
; Fekih, A . ; Lusinchi,
X.
Tetrahedron Lett, (1985),
PhCNH2,
CH-CHCH3
r
Ph
Tetrahedron Lett, (1984),3,293
M.
2. PyH*OTs 3c
.Ph
1
*
RT
1. NaHTe,
0
/ \
-
259
O L E F I N S FROM E T H E R S
0°C
CF3COOH,
CH2C1
P
26,
nC5H1
Miyake, J.; Murai, S.;
CH=CHCH3
74%
10 rnin
Ogawa, A.:
6197
3c
Sonoda, N . Tetrahedron Lett, (1985),
26,
669
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
260
-
Sulfonates
SECTION 205: Olefins from Halides
-
SECTION 205
I
,
CH 2=CH
N iI
( PPh3 )
> 8 0%
R o l l i n , Y.: Meyer, G . ; Troupel, M.; Fauvarque, J . - F . ; J.
--JCS Chem Cam,
MeOH,
Br
@= Janout,
1% dvb,
(1983), 793
50°C
*
3.5h
@CH2S-Naf,
Perichon,
9 5% ( 9 9 ) c o - d i v i n y l benzene]
poly[styrene
v.;
v
Cefelln, P.
1.
Tetrahedron E ,(19831,
(PhTe)2,
NaBH4,
2,391 3
EtOH
r e f 1ux 2.
Br2,
CC14,
3 . a q . NaOH,
0°C 25°C
3h
Uemura, S. c1
I
* : Fukuzawa,
S.
---J Am Chem Soc,
1 . CH2=CHBr,
,
NiC12, Et20
PPh Me2N-CH C H \ CH2SMe
PhCHCH3
62%
, RT
(19831, t
105,2748 PhCHCH=CH2
90% (23% ee, S ) 1 0 % HC1, j 0 C G r i f f i n , J.H.; Kellogg, R.M. J Org Chem, (1985), 50, 3261 2.
SECTION 205
OLEFINS FROM H A L I D E S
261
1 . Mg, E t 2 0 p
cat.
h
CI
2.
y
ZnC12,
3 . CH2=CHBr,
THF/Et20
cat.,
Ph
*
THF/Et20 0°C
9 5% (85% ee, S )
=
*
Hayashi, T.; Hagihara, T.; Katsuro, Y.; Kumada, M. will Chem Soc *,(1983), 56, 363 Hayashi, T. Konishi, M.; Okamoto, Y.; Kabeta, K . ; Kumada, M. J Chem, (1986), 2,3772
---
*:
I
Br
1 . C8K,
I
PhH, R T ,
8h
2 . EtOH
PhCHCH2Br
t
3 . HOH C8K = g r a p h i t e powder/200°C/K Rabinovitz, M.
* ; Tamarkin,
Br I PhCHCHPh
I
B r
D.
PhCH =CH 8 0%
Syn Cornnun, (19841,
a q . Na2S.9H20,
111, 377
PhCH3 PhCH=CHPh
-t
Bu3P+C1 6 H 3 3 B r 25OC, 9 5 r n i n
quant.
Landini, D.*; Milesi, L.; Quadri, M.L.: Rolla, F. J Org Chem, (19841, 49, 152
9
Hrubiec, R.T.;
-
1. nBu2CuLi, -2OOC 2 . HOH
Smith,
* M.B.
-
Et20
\/ e
~-Bu
(E:I =
-
80%
2:l)
J Org Chem, (1984) , 3, 385
262 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 205
n B u 4 S n , Pd(PPh3)4 2 L i C 1 , T H F , 70°C
t -Bu
S c o t t , W.J.: C r i s p , G.T.;
Br
1B r
Davies, S.G.
*
1 5 min
* ; Thomas,
80%
S t i l l e , J.K. J Am Chem Soc, (1984), ----
Cp2TiC1 2 y T H F
I
nPrCHCHCH3
-
t-Bu
41h
S.E.
106,4630
t
9 5%
Synthesis, (1984), 1027
1 . L B u L i , T H F , -78°C NNHTRIS II Li2CuC1 CH~C(CH~)~C~ 2. O"C, 10 m i n Charnberlin, A.R.
*
Bloom, S.H. Tetrahedron
Br
nPrCH=CHCH3
66%
E ,(1984) , 25, 4901
1 . HOCH2SO2-Nat-2H20 Te, EtOH, NaOH, 70°C 2 . 2M H C 1
Suzuki, H.
* ; Inouye,
M.
Chem Lett, (19851, 225
77%
SECTION 206
263
OLEFINS FROM HALIDES
Q I
6e3
CH2=CHSiMe3, P d ( O A c ) *
PPh3 5 0 ° C , 5h
AgN03, C H 3 C N ,
NEt3,
*
67%
Karabelas, K.: Hallberg, A. Tetrahedron Lett, (1985), 26, 3131
-
1 . i B u 3 A l , 30 m i n *--/
Br
Ni(MeSa1 )2
e
2 . d i l H2S04 MeSal = !-methyl
-+-. i-BU
pentane, RT
91 %
salyc i l a l dimine
Caporusso, A.M.*; Da Settimo, F.: Lardicci, L. Tetrahedron Lett, (1985), 26, 5101 (Me3Sil3MnMgMe
BrC h = C H P h
(I)
Fugami, K.;
-
Et20/THF, -78"C,
3h
>
PhCH=CHSiMe3
(2)
Oshima, K.*,' Utimoto, K.: Nozaki, H. Tetrahedron Lett, (1986),
70%
2,2161
-
SECTION 206: Olefins from Hydrides
No Additional Examples For conversions of methylenes to olefins (RCH,R' Section 200.
+
RR'C=CH,, see
264 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 207
SECTION 207: Olefins fran Ketones
0
+-
II
( M e S ) 2BCH2
PhCPh
t
Ph2C=CH2
75% Pelter, A . ; Singaram, B . ; Wilson, J.W. Tetrahedron E ,(19831, 24, 635 0
C p 2 T i C H 2 .ZnI
II
PhCPh
Eisch,
PhCH3,
* J.J. ; Piotrowski,
t
-1OOC
Ph2C=CH2
78% A.
-
Tetrahedron Lett, (1983), 24, 2043
Cp2Ti 0°C
Et20,
-
t
RT
Bh Clawson, L.;
Buchwald, S.L.; Crubbs, R.H.
Bernard, M.; Ford,
*
-
Tetrahedron Lett, (19841,
* W.J.
0
84%
25, 5733
99%
--J Org Chem,
(19831, 48, 326
SECTION 207
265
O L E F I N S FROM KETONES
1 . N H 2 N H S 0 2 P h , MeCN-HC1 2.
2.2 E B u L i ,
3.
0°C
-8°C
t
4 . EBuBr, 2 0 ° C overnight Chamberlin, A.R.
Baba, T.:
*; Liotta,
50%
E.L.; Bond, F.T.
Org Syn, (19831,
* --Bull Chem Soc s,(19831, 56,
82%
Avasthi, K.; Suzuki, A.
2. d e c a l i n ,
2h Mohmadi, F.: C o l l m , D.B.
*
92%
THF,
-7aoc
t-Bu
82%
* S. ; Delorme,
25, 271
Tetrahedron Lett, (1984),
Me
KDA,
1571
160°C
0
Hanessian,
61,141
ii
t
t-Bu (95
D . ; Beaudoin, S.;
---J Am Chem
Leblanc, Y .
-
:
Soc, (19841, 106, 5754
t-BU
5)
266 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 207
84%
Murayama, E . ; Kikuchi, T.; Sasaki, K . ; Sootme, N . ; Sato, T . Chem Lett, (19841, 1897
--
1 . LDA
0
II
CH3(CH2)9CCH3
Takai, K . ; Sato, M.:
t
E t
2.
C1-b(OPh)2 0
3.
2 Et3A1,
25°C
Pd(PPh )
,
*
I
C H ( C~ H 2 ) g~~ = C H ~
71%
3h
Oshima, K.'; i o z a k i , H. B u l l Chem Soc Jpn, (19841, 57, 108 ----
tBuO-K',
Ph3PMe,
PhH
100°C,
2h 91 %
add k e t o n e t o m i x t u r e t
F i t j e r , L. ; Quabeck, U.
-Syn Comrmn,
(1985),
3,855
0
1. LiN(TMS)2 2. B E t 3
3 . CH2=CHPPh3+Br4 . KOH
Posner, G.H.
t
; Lu, S.-B.
J Am Chem ----
*
ph$?:"2
-
Soc, (19851, 107, 1424
69%
SECTION 209
1 . C1CH21, -78
MeLi
- -60°C
-
2. Li, -60
Barluenga,
267
O L E F I N S FROM O L E F I N S
t
20°C
* J. ; Fernandez-Simon, J.L.: Concellon, J.M.; JCS Chem Comn, (1986), 1665 ---
8 0%
Yus, M.
Review: "Titanium Induced Dicarbonyl-Coupling Reactions1'
McMurry, J.E.
*
Accts Chem Res, (19831, 16,405
I -
Related Methods: Olefins from Aldehydes (Section 199) 208: Olefins from Nitriles SECTION 1 . LDA,
CN
THF,
-78°C
2 . nBu3SnCH21,
I
"C12H25CHCH3
3.
MeLi, THF,
*
-78
LiBr/Et20
Me
- 0°C t
I
"C1 2 H 2 5 C = C H 2
-20°C
83%
4 . a q . NaOH
Pearlman, B.A. ; Putt, S.R.; Fleming, J . A . --J Org Chem, (1985), 2,3625 SECTION 209: Olefins from Olefins 1. nBu3SnLi PhS02CH=CHnC8H1
2.
CHC13, S i 0 2 t 6OoC,
Ochial, M.; Ukita, T.: Fujita,
* E.
nC8H1 7 C H = C H
17h
2
78%
JCS Chem Ccnun, (19831, 619 1 457
C h e m m t T 9 8 3 1, --
268 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
FP+
1 . CH2C12, HBF4.0Et2,
cH IcH I
2 . NaI, a c e t o n e
I
3 . HC1,
(CH2)4
4 . "BuNI,
CH1Cy2 FP
Lennon, P . ; Rosenblum, M.
4
0°C
CH2C12, RT, 4 h C H 2 C 1 2 , RT
52%
* 2 Am
2h
v
(Me3Si)3A1.0Et2
; Yoshida,
J . ; Lautens, M.
J Am Chem ----
Soc,
105, 1233
72%
reflux x
YiMe
Chem Soc, (1983),
M o ( C O ) ~ , PhCH3,
Trost, B.M.
SECTION 209
(E:l (1983),
/
= 2:l)
105,4494
C p 2 T i C 1 2 , THF iPrMgBr, 20°C
7 6%
lh Lehmkuhl, H.
* ; Tsien,
ll
Y.-L.
*
3(
16%
Chem Ber, (1983), 116, 2437
1 . Cp2Ti
t 2 . PhCPh, PhH, RT, 1 2 h I1
0 Buchwald, S.L.;
Grubbs, R.H.
* ---J Am Chem
80%
Soc,
(1983),
105,5490
SECTION 209
N0
I
-
CH3
Ono,
Et,OL
-30°C
* N. ; Hamarnoto,
PhCH2CH=CHCH3
6OoC,
* ; Viout, P.
c
CH 3
I CB u CH CH = C C H
cl
,C.02Et
7 6%
RT
15h I.; Kaji, A .
10 KOH,
D'Incan, E.
-
269
OLEFINS
nBu 2CuL i
CH =CH - C CH 2 C H C O 2 E t* - .
I
FROM
OLEFINS
( -E :_Z = 8 8 : 1 2 )
--JCS Chem Comn, (19841,
DME 30 min
*
274
PhCH =CHCH2CH3
95%
Tetrahedron, (1984),
$0,4321
- s i : e 2 8
PhMe2SiMgMe
ZPh
cu I
1-
O"C,
12 min
(95
*
Morizawa, Y.; Oda, H.; Oshima, K. ; Nozaki, H.
-
Tetrahedron Lett ,. (19841,
1 . O=S=NSO P h ,
2
0 - 20"C,
2 . EtMgCl,
5) 74%
3,1163
Et20 10h
CuBr/Me2S
*
3. aq. H+
*
Deleris, G. I Dunogues, J.; Gadras, A .
Tetrahedron Lett, ( 1984),
80%
25, 21 35
270 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
PhHgCl , CuCl (PhS02)2C(CH2CH
L
L
* Trost, B.M. ; Burgess, K.
10% P
SECTION 210
PhS02
P Y B n
L
THF R T
50%
JCS Chem Camn, (1985), 1084
- 6
S0,Ph
DMF
PhSO2Na*2 H20,
6"O'
5% Pd(PPh3)4,
20°C
70%
1 Oh
t
Ono, N. ; Hamamoto, I.; Kawai, T.; Kaji, A.; Tamura, R.*: Kakihana. M. B u l l Chem Soc *, (1986), 405 --* Tamura, R.*; Hayashi, K.; Kakihana, M.; Tsuji, M.; Oda, D.; Scholz. D . Tetrahedron Lett, (1985), 26, 851
z,
SiMe, SO,Ar
1. nBuLi, 2.
THF,
-78
- 0°C
a q . NH4C1
*
Padwa, A. ; Wannamaker, M.W. Tetrahedron Lett, ( 1 9861,
90%
3,581 7
-
SECTION 210: Olefinz from Miscellaneous Compounds NaTeH,
RT,
*
EtOH
lh
Osuka, A. ; Shimizu, H.; Suzuki, H.
*
86%
Chem Lett, (1983), 1373
SECTION 210
OLEFINS FROM M I S C .
271
1 . NaH, E B u L i
0
II
PhCCH2S02Me
2 . cC8H171
Scholz, D.
7 5%
reflux
EtOH,
Liebigs Ann Chem, (1 9831, 98 1 . EBuLi,
0
II
PhCH2SPh
II
0
Engman,
L
4 . NaOEt,
*
nC8H1 7CH=CH2
+
N a O H , Br,
3.
THF,
0°C
2.
24% T e ,
RT,
3.
50% a q .
AcOH
* -J Org C h m , L.
NNHTs
( 1 9841,
3h
90%
(I:E =
Ph
diglyme t
PhC(CH2)40H
2.
Harada, T.; Akiba, E.: 651
8OoC,
Oku, A.
6h
*
-
Varbene Complexes i n Organic SynthesisfT
---
Angew Chem Int Ed -,
(1984),
"The Peterson Reactionf' Ager, D.J.
*
Synthesis, (19841, 384
"Recent Developments i n Alkene Chemistry" Pasto, D . J .
*
74%
Tetrahedron Lett, (19851,
Reviews : D B t z , K.H.
2:8)
2, 3559
1 . 2 . 2 KH,
II
PhCH =CH Ph
t
Tetrahedron, (19841,
2, 2805
23, 587
26,
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 15 PREPARATION OF OXIDES
This Chapter contains reactions which prepare the oxides of nitrogen, sulfur, and selenium. Included are g-oxides, nitroso, nitro compounds, nitrile oxides, sulfoxides, selenoxides, and sulfones. Oximes are found in Sections 60A (Protection of Aldehydes) and 180A (Protection of Ketones). Preparation of sulfonic acid derivatives are found in Chapter Two and the preparation of sulfonates in Chapter Ten. Oxides from Acetylenes - --
SETION 211
No Additional Examples
---
SECTION 212: Oxides from Acid Derivatives
No Additional Examples
--
SECTION 213: -Oxides from Alcohols and Thiols
PhCH2CH2S-Na
2 . KMn04,
a q . AcOH
3 . N a B H 4 , MeOH 4 . BnBr
* Ueno, Y. ; Kojima, A . ;
Okawara, M.
*
BnS02Bn 84%
Chem Lett, --
SECTION 214: Oxides from Aldehydes
--
No Additional Examples
(19841, 2125
SECTION 215
O X I D E S FROM A L K Y L S
273
SECTION 215: -Oxides from Alkyls, Methylenes, and Aryls CH3S02F,
-
50°C
Hyatt, J . A .
A 1 C1
RT,
l h
*
91 %
* ; White, A.W.
Synthesis, (19841, 214
PhS03H,
PPA
*
'2'5
Sipe Jr.,
so2 Me
* H.J. ; Clary, D.W.:
White, S.B. Synthesis, (1984), 283
+SO~H 20"C,
56%
. H ~ O
24h
CH3S03H-P205 95%
*
Ueda, M. ; Uchiyama, K.; Kano, T. Synthesis, ( 1984) , 323 FeN03-K-10 c l a y THF,
20h
*
3 9%
41 %
NO,
Cornelis, A . ; Laszlo, P. ; Pennetreau, P. Bull Chem Soc Belg, (1984), 93, 961 ---
274 C0MPEM)ILJM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 217
Si02, CAN pet ether,
* Chawla, H.M. : Mittal, R.S.
PhH
6 NO 2
65%
Synthesis, (19851, 70 F
HN03-S i 0 2
&NO:
CH2C1
40%
Tapia, R.; Torres, G . : Valderrama, J.A. Syn Ccxunun, (19861, --
42%
16,681
NO2
SECTION 21 6: --Oxides from Amides
No Additional Examples SECTION 217: ---Oxides from Amines
- ,oo,
(HO)*B,
00’
-
B ( O H ) 2 2Nat.6H20
5 0 % a a . MeOH
*
McKillop, A . ; Tarbin, J.A
H
Mitsui, H.; Zenki, S.:
t
Tetrahedron Lett, (19831,
H2°2 Na2W04
*
* Shiota, T.: Murahashi, S. JCS Chem Comn, ---
(19841, 874
92%
9,1505
oj, +Y -
0
68%
SECTION 219
275
O X I D E S FROM E T H E R S
SECTION 218: Oxides from Esters
No Additional Examples
-
SECTION 219: --Oxides from Ethers, Epoxides,
,oo, PhSCH3
( H O ) 2B,00,B
(OH)
50% a q .
* McKillop, A. ; Tarbin, J.A
PhSCH3 + 74%(1 eq)
-
Tetrahedron Lett, (19831,
1
CH3N02,
+
2,1505
COOH
0
,
4h
Helv Chim Acta, ---
Bu4N
PhSCH3 94%(excess)
0
*
It
P h C=CS M e
R u C ~ ~ ( P P ~ ~ ) ~
Miiller, P . : Codoy, J.
B n S C H 2 C H 2CH * B r
0
I1
II
w
4 P h C=CSM e
0
*6H20
MeOH
and Thioethers
aq. HN03
AuC104-
(19831,
t
66,
1790
0
II
B nSCH 2CH 2CH *B r
4h
GasDarrini, F.: Giovannoli, M.; Misiti, D.; Natile, C.; Painieri, C. Tetrahedron, (19831, 2,3181
89%
276 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 219
OH I
0
CH 3CHOOOH -4O"C,
I1 Pr- S - Pr
t
Pr-S-Pr 30 min
no y i e l d Shereshovets, V.V.; Komissarov, V.D.; Shafikov, N.Ya.; Bachanova, L.A.; Kolosnitsin, V.S.; Nikitin, Yu.E.: Tolstikov, G.A. -J Org Chem USSR, (19831, 2, 207
Ph-S-iPr
2 . HOH
Palmieri, G.
\I
P h - S - i Pr
t
* Gasparrini, F. ; Giovannoli, M.;
93%
Maresca, L.; Natile, G . ;
~ C o m n u n ,(19841, 14, 1 1 1 1
tBuOOH,
PhCH2-S-CH3
0
1 . CH3N02, a q . HN03 a q . H2S04, R T , l h
-
( + ) - d i e t hyl t a r t r a
CH2C12,
, .o
Ti(OiPr)4
-77"C,
tk
P h C H -'S
*
-CH
7 0%
24h
DiFuria, F.; Modena, G.; Seraglia, R.
;
(46% ee) Synthesis, (1984), 325
Ti(OiPr)4, LBuOOH Ph-S-CH3
( R , R ) - d i e t h y l t a r t r a t e>
H O H , -20° C
P'h:/
CH 80%
( 8 9 % eed R ) Pitchen, P. ; Duzach, E. ; Deshmukh, M.N. : Kagan, H.B. J Am Chem Soc, (19841, 106, 8188 *---Tetrahedron Lett, (lm), 25, 1049 Pitchen, P.; Kagan, H.B.
SECTION 220
p" Me3SiOC=CH2
O X I D E S FROM ETHERS
1 . PhN=O,
CHC13,
1 N H C 1 , THF, 2 0 ° C
3.
Ag20,
Sasaki, T.; Mori, K. ; Ohno, M.
P-
20°C
2.
PhH,
*
(+)-diethy1
0
P hCCH=N - P h
80%
Synthesis, ( 1 9851, 279 0
*.
% ",,
*
*
Nouv J Chem, (1985), --0
80 % S)
967
SECTION 220: --Oxides from Alkyl Halides and Sulfonates
No Additional Examples
R)
2, 1
( 4 0 % ee,
Imarnoto,
Q
60%
tartrate
* T. : Koto, H. -Chem Lett, (19861,
/
PhH'S
t
( 9 5 % ee,
Dunach, E. ; Kagan, H.B.
0
t
I1
t
20°C
T i ( O i P r ) 4 , a q . LBuOOH C H 2 C l 2 , - 2 O " C , 1Gh
S-Ph
277
278 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 224
SECTION 221 : -Oxides from Hydrides 1 . HgC12,
PhS02Na, HOH RT
2.
50% aq.
NaOH/dioxane
82%
RT Sas,
W.
JCS Chem Comn, (1984), ---
+
6
862
-
N H 4 N O 3 , CH2C12
( C F 3 i ) 2 0 , HBF4 0 35°C
Bloom, A.J.: Mellor, J.M.
*
7 0%
-
Tetrahedron Lett, (19861,
SECTION 222: -Oxides from Ketones
No Additional Examples SECTION 223: -Oxides from Nitriles
No Additional Examples SECTION --224: Oxides from Olefins
No Additional Examples
3, 873
SECTION 225
OXIDES F R O M
279
MISC.
SECTION 225: -Oxides frcm Miscellaneous Compounds 1. NaOH
2 . AgN03, NaN02
t
NO2
*
Kornblum, N. ; Singh, H.K.;
Kelly, W.J. Chm, (19831,
J Org
b
2. M e 1 Chou, T.
* ; You,
M.
48,
332
CH3S02( C H 2 I 4 i P r
7 4%
Tetrahedron Lett, (19851,
-
26, 4495
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
CHAPTER 16 PREPARATION OF DIFUNCTIONAL COMPOUNDS
-
SECTION 300: Acetylene
iH3 H C-C C H 0A c
T
Co2 ( C O ) 6
-
Acetylene
1. nBuC=C-)3Al, 3h C H 2 C 1 2 , -78 - 0 ° C
2. CAN, acetone
*
e
CH 3 I H C S C C H C r CnBu 5 5%
Padmanabhan, S . : Nicholas, K.M. Tetrahedron Lett, (19831,
PhCH=C
\
-
Ph(Ph2PCH2CH2PPh2)2 Br
P h H , C O , 5N N a O H t
B n N E t 3 C1
-
* H.
*
2,2239
F I CmC -CSCPh
Galamb, V.: Gopal, M.; Alper, Organometallics, (1983
54%
,2, 801
1. nBuLi 2. Z n C 1 2 3. ICH=CHCl, THF 4. N a N H 2 / N H
Negishi,
* E. ; Okukado,
3(1)
67%
N.: Lovich, S.F.; Luo, F.T. -J Org Chem, (1984), 9, 2629
SECTION 301
-
ACETYLENE
OT f
tB U
I
CH C S C = C HC H
55"C,
*
30 m i n
281
*
C H C S C - C E C CH
Pd(PPh,), CH3cCH2C1, 0
, CuI NEt3,
t PhH
n B u C S C - C E C n-B u -
Rossi, R.; Carpita, A.; Bigelli, C. Tetrahedron Lett, (19851, SECTION 301: Acetylene
-
MeCN
2. Me-C=C-SiMe3
TiC14, 3 . HOH J e l l a l , A.; Zahra, J . - P . ;
*
CH2C12
(fH2)lO CECH
*
*
EtNH2
*
2. I C G C ( C H ~ ) ~ M M ~ ,e O H / E t 2 0 NH20H *HC1 36%
Singh, A. ; Schnur, J.M.
26, 523
0 ye II M e C % CH C C N Me 55%
Santelli, M. Tetrahedron E, (1983),
1 . a q . KOH, C u C 1 , E t N H O H mHC1
CZCH I
54%
CarbOXyliC Acid
1 . Cu2CN2, Me2C =CHCC 1
3
85%
Synthesis, (1985), 962
Stang, P . J . ; Dixit, V.
nBuC%H -
ACID
Cornnun,
(1986),
2,1395 C H 3 (CH\2 ) 7 C 111 C I
C C 111 /
HOOC ( C H 2 ) 1 0
16,847
282 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 SECTION 302: Acetylene
-
* : Sugahara,
Kuwajirna, J.
Alcohol, Thiol
2.
89%
S.; Enda, J.
Tetrahedron Lett, (1983),3, 1061
CH2C1 2 . - 7 8 ° C
CH3CZCSiMe3
PCC
* (87% ee)
Johnson, W.S.*; E l l i o t t , R . ; E l l i o t t , J . D .
J Am Chem ----
e>-CH2A1
Soc,
C1 2 ,
RT,
(19831, 105, 2904
Et20
I!
nB u C=C C E t
76%
H
3. K O H , a q . MeOH
0
SECTION 302
OH
>
4h
I
nBuCSCCHEt
78%
*
Giacornelli, G. ; Lardicci, L.; Palla, F.
( 6 4 % ee,
R)
J Org Chem, (19841, 2, 310 --___
1. tBuLi,
THF
OH
-90°C nC6H, 3CH=C=CH2 -
*
2.
ZnC12,
3. EtCHO 4 . H,Of
Zweifel, G. ; Hahn, G, Hahn, G.; Zweifel, G .
3
-74°C
*
Et
/\/cEC
(erythro:threo
H 95% "'gH1 3 = 4:96)
Chem, (1984), 49, 4565 Synthesis, (1983), 833
--J Org
SECTION 302
ACETYLENE
-
ALCOHOL
283
1 . excess EBuLi TH F # O
7
\u;
H
Sayo,
H0"
2 . HOH
HO
H
2)
(98
N.; Shirai, F.;
* Nakai, T. : Kitahara, E. Chem Lett, --
90%
(1984), 255, 259
THF/Hexane, reflux
*
Utimoto, K. ; Lambert, C.: Fukuda, Y. Tetrahedron
v "'CZC, 71 %
s, (1984), 25, 5423
1 . LBuLi
CH C Z C CH
3
2. Ti(OiPr)4, THF 3-
*
O C H O
CH3CSCCH2CH 80%
Furuta, K.; Ishiguro, M.; Haruta, R.: Ikeda, N.; Yamamoto, H. will Chem Soc Jpn, ( 1 984), 3, 2768
---_
t B u C3C - 6
Brown,
1 . EtCHO, pentane 25OC, 15 m i n
2 . HOCH2CH2NH2
*
OH
1
tBuCECCHEt * 83%
* H.C. ; Molander, G.A.; Singh, S.M.; Rocherla, U.S. J Org Chem, (1985), 2, 1577
284 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
PhCHO, nBuCGC1
DMF,
OH
CrC12
I
t
2h
25"C,
SECTION 302
nB u C E C C H P h
82%
* Y Takai, K. ; Kuroda, T.; Nakatsukasa, S.; Oshirna, K. ; Nozaki, H. Tetrahedron L e t t , (1985),
0
26, 5585
1 . CH2=C=CHB(0H)*
!I
5
PhCHCH2CCH3
I
8,
sieve,
Et20
*
H & ".'
HO
H OH
2 . H202/NaOH
OH
9 5%
*
(99:l)
Ikeda, N.; Ornori, K.; Yamamoto, H. Tetrahedron Lett, ( 1 9861, 3, 1 1 75
TiC14,
*
CH2C1 -78°C
8 5%
Danheiser, R.L. ; Carini, D.J.; Kwasigroch, C.A. --J Org Chem, (1986), 51, 3870 1 . LiC=CnC
H 6 13
3 . NaOH/H202
I
0 i -Pr
*
*
HO(CH2)5CSCnC6H1 71 %
Brown, H.C. ; Basavaiah, D.; Eihat, N.G. --J Org Chem, (19861, 51, 4518
SECTION 305
-
ACETYLENE
285
AMINE
OH
1 . 2 HCsCCH2Br 2. PhCHO
Pb,
I
Bu4NBr
TMSCl,
PhCHCH=C=CH2 ( 4 )
*
DMF
t
PhfHCH2CsCH ( 1 )
3 . a q . HC1, A c O E t
OH
Tanaka, H.; Hamatani, T.; Yamashita, S.; Torii, S. Chem Lett, (19861, 1461 -SECTION
303: Acetylene -
95%
*
Aldehyde
No Additional Examples
-
-
SECTION 304: Acetylene
Amide
No Additional Examples SECTION
305: Acetylene -
Amine
1. FBuLi PhCSCH
2.
B F 3 * O E t ? , THF,
-78OC
3.
&”,
, -78°C
4.
LiA1H4,
-78
*
Yamaguchi, M. ; Hirao, I.
-
Boche,
I
Me
8 0%
Tetrahedron Lett, (19831,
Me2N-S03Me
-Ph
N +C=C
-1OOC
PhCGC-)3CuLi2
* G. ; Bernheim,
>
n
*
2, 1719
P h C E C N Me
83%
M.; Niessner, M.
Angeu Chem Int Ed -, ----
(19831,
22, 53
286 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
N-Bn
1 . [PhC=CLi/SF3.0Et2] THF, -78°C - RT
II
H-C-EPr
2. a q . NaOH
Wada, M.; Sakurai, Y.;
* Akiba, K.
SECTION 306: Acetylene
-
SECTION 307
NHBn
I
*
nPrCHECPh
60%
Tetrahedron Lett, (1984), 25, 1083 Ester
No Additional Examples SECTION 307: Acetylene
Ph3P=CHSMe Braga, A.L.;
-
Ether, Epoxide, Thioether
0 II 1 . PhCCl, PhH, RT
2. 230"C, 0.005 mmHg
*
* Comasseto, J.V. : Petragnani, N.
Tetrahedron Lett, (1984),
t
25,
11 11
*
2 . [ L i C z C n C 5 H , /Et2A1 C1 ] 8 0 ° C , 2h
* ; Martin, S.J.
49%
-
1 . MeS-SMe2 BF4 RT, DCE, 15 min
Trost, B.M.
P h C=C S M e
J Am Chem ----
Soc,
88%
(1984), 106,4263
SECTION 308
-
ACETYLENE
0 I1
1. 2.
nBuCECCCH3 -
"'+m
HO
TsOH,
OH'
Dibal-H, O"C,
287
ETHER
"'on"
Py
CH2C12
t
l h
,,,-BusG
A
90%
3. a q . HC1, 0°C
-: S- = 9 6 : 4 ) (R
*
Ishihara, K.; Mori, A.; Arai, I.: Yamamoto, H. Tetrahedron Lett, (1986),2, 983 1. PBr3, H C E C C H 2B r
THF
Py,
t
2 . BnOCH2C1, A1
BnOCH2CH2CECH
53%
TH F
Bull Chem Soc Fr, (19861,I1245
Guedin-Vuong, D.; Nakatani; Y. SECTION 308: Acetylene
-
Halide
0
1 . P(OEt3)3
II
2 . CBuLi,
CF3C F2C F 2 C C l
*
CuI
3. T B A F , THF
C F3C F2CsCH
RT
89%
Ishihara, T. ; Maekawa, T.: Ando, T.
-
Tetrahedron Lett, (19841, 25, 1377
1 . 12'
C H 3 C H = C =CHHg I
t
-40°C
2 . 3M N a 2 S 2 0 3
3 . 1N HC1
* Larock, R.C. ; Chow, M.-S.
I
I
h
c
CH3C HC Z CH 85%
Organmtallics, (19861,2, 603
288 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
-
309: Acetylene SECTION -
Ketone 0
cC6H13 C S C S i M e 3 -
1
CH 3
Kawanami, Y.;
nPrCHCC=CnC6H1
- 1
2 AgBF4, CH2C12 RT, 3 0 m i n K a b u k i , T.; Yarnaguchi, M.
*
THF,
2 . BF3*OEt;,
C=CH
-78°C
3 . A c ~ O , THF,
* ; Rocherla,
U.S.;
Chem Lett, (19831, 35
n II
+ C H ( C H ) 5C=C C C H 72%
Singh, S.M.
Tetrahedron Lett, (19841, 25, 2411
BH-HC1 4 M e 2
2 . LiC=CnBu,
-78°C-RT
*
3 . NaOH/H202
* ; Bhat,
CsCCPh
-78°C
B B r 3 /p e n t a n e
Brown, H.C.
II
84%
1 . E B u L i , THF, - 7 8 ° C 2 . B F 3 * O E t 2 , -78°C
1.
nB u C E C B r
"C5H1
-78OC
*
( c H ) C=C H
0
t
Yamaguchi, M. ; Waseda, T.; Hirao, I.
Brown, H.C.
91 %
-78°C
3 . PhCNMePh, THF
!
cH
Me
Tetrahedn>n Lett, (19831, 2, 5131
1. nBuLi, nC 5 H 1
II
t
nPrCHCSEt
SECTION 309
-
62%
N.G. ; Basavaiah, D.
--Israel J
0 nBuCECCCH2nBu II
Chem, *I(
S thesis, (19831, 885 .72
SECTION 311
ACETYLENE - OLEFIN
1 . E B u L i , CH2C12, -78°C 2 . VC13, CH2C12, -78°C
n B u CECH
3. P h C H O , - 7 8 ° C
-
289
0
II
reflux
*
nB u C f C C P h
71 % * Hirao, T. ; Misu, D.; Agawa, T. Tetrahedron Lett, (1986), 3, 933
-
SECTION 310: Acetylene
-
Nitrile
No Additional Examples SECTION 31 1 : Acetylene
-
CGC(CH2)90THP
1
C?CSiMe3
-
Olefin
1 . Li(A1HiBu2nBu) DME/hexane,25"C 2 . 3N HC1
THPO(CH2)9CH=CH I 3 . KF.2H20, D M F n C H C S C - 3- .7 4. n B u L i , h e x a n e / d i g l y m e nC H B r 81 % - 3 7
>
Miller, J.A.; Zweifel, C.
e2
B CH = CHnB u
(L)
*
__-J Am Chem Soc,
1 . aq. NaOH, THF 0°C
> -nBuCECCH=CHn-Bu
2 . Cu(acac)2 3. B r C Z C n B u , - 1 5 ° C
Hoshi, M.; Masuda, Y.;
9, 1383
(19831,
* Arase, A. --will Chem Soc @,
(L)
75% (1983),
56,
2855
290 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 311
1. 2 CBuLi, Et20 -78 - - 4 5 ° C M e 0 CH C S C H O M e
Koshino, J.;
C s TMS
I
CECnC
H 6 13
(_?.C7H1 5 ) 3 B y T H F
-7 8 o c-RT
3 . AcOH, RT, 4 . 3N NaOH
nC7H1 5CSCCH=CH 2 88%
2h
* Sugawara, T.; Suzuki, A .
sy" Commun, (19841,
1 . DBE,
Zn,
EtOH
*
2 . NaOH, MeOH
Aerssens, M.H.P.J.;
I nC6H1 3CH=CH
JCS Chem Comn, (1984), 735
CH = C H CH =C H CH~(CH~)~CSCH t RuH2(PBu3)4 P h H , 8O"C, 2 h
Watanabe, H.; Watanabe, Y.
HCZC
70%
* Brandsma, L.
* Mitsudo, T. ; Nakagawa, Y.i
2,245
C H 3 ( C H 2 ) 5 C = "-L CH = C H E t
88%
Watanabe, K.; Hori, Y.; Misawa, H.;
J Org .-Chem, -
(19851,
50, 565
1 . E B u L i , nC6H13Br 2 . Et2A1C=CnC 5H1 1 Me2C=CHCH2S02Ph
DCE,
AlC1,
t J
Et20, r e f l u x
Trost, B.M.
* ; Ghadiri, M.R.
---J Am Chem
HCCHC=CnC5H1
I
IICgH13 Sot, (1986),
71%
108,1098
SECTION 31 2
-
ACID
-
-
SECTION 312: carboxylic
1 . 2 LDA,
2.
carboxylic
THF
-78°C
nBuCH2C02H
-
1 2 , THF,
*
29 1
ACID
nB uCH C O O H
RT
-- 1
>
nBuCHCOOH
-65°C-RT
overnight
Belletire, J.L. ; Spletzer, E.G.; Pinhas, A.R. Tetrahedron Lett, (19841, 1.
02'
MeCN,
-
82%
25, 5969
10°C
9,w-d i c y a n o a n t h r a c e n e
*
Ph-Ph 2. H202
88%
*
Schaap, A.P. ; Siddiqui, S.; Prasad, G.; Palomino, E.; Sandison,
M.
Tetrahedron, (19851,
R
1 . C12CHCC1,
NEt3
2 . E B u L i , THF,
3 . Ac20,
-78'C
4. NaI04, CC14, 5 . aq.
6.
5,2229
Ru02,
-78°C
-
RT MeCN
HOH
NaOH
aq. H
82%
-I
*
Depres, J.-P.; Coelho, F.; Greene, A.E. -J Org Chem, (19851,
50,
1972
292 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
--
SECTION 313: Carboxylic Acid
3
Q
1. 0-NS-CN, 2. He,
SECTION 313
Alcohol, Thiol
0°C
*
Ni(R)
QCYOH
3 . H5106
4 5%
t
J Org
Kozikowski, A.P. ; Adamczyk, M.
Chem, (1983),
48,
366
1 . CH2=CHPh
+ -
H2, N i ( R ) A 1 C 1 3 , a q . MeOH
2.
3. NaI04, 4 . CH2N2
Ph H
H O O C G OH
NaHC03
90%
(_R : _S = 1 : 1 ) Kozikowski, A.P.*; Kitagawa, Y.; Springer, J.P. JCS Chem C a m , (19831, 1460 ---
b
5.76
NaOH,
1 5 mmol Cu, 0 . 6 6 CC14,
t
Sasson, Y. ; Razintsky, M.
"'fY O Y O fic8H1 7
2 3 0 . 4 9 HOH
1 . TiC14,
80°C 6h
2. 3.
CF3COOH *HOH Jone's Oxidation
4.
KOH/HOH
COOH
87%
JCS Chem Comn, (1985), ---
CH2C12
* Elliott, J..D. ; Steele, J.:
>
nC H -
1134
" Y C O O H
H
Johnson, W.S. Tetrahedron Lett, ( 1 9851,
OH
7 6%
26, 2535
SECTION 313
ACID
- ALCOHOL
1. nBuLi,
oc CP
\ /
F(
e,,#,
'%
THF,
2 . Et2A1C1,
PPh3
3.
cc II
4.
EtCHO,
293
-78OC
-40°C ti Me
-10°C
>
2 CBuLi
HOOc%Et H0 ""'
5. M e 1
0
6. oxidation
no y i e l d
*
Davies, S.G. ; Dordor-Hedgecock, I . M . ; Warner, P . ; Ambler, P.W. Tetrahedron Lett, (19851, 26, 2125, 2129 * Davies. S.G. : Dordor. I . M . : Walker. J.C.: Warner. P. * ' Tetrahedron Lett; ( 1 984) 3, 2709 Davies. S.G. : Dordor.. I.M.: Warner. P. --J& Chem &, (1984), 956
-
cp
,
1
1 . LDA
1/ c c H 3 ",,,
Ph,P J
2.
MX
_______)
ti o
;
HO ,$Et
E t $OH
, c A H
" 0 2 C d H
3. EtCHO
"%,
4. o x i d a t i o n F1X
=
MX
= SnC12
iBu2A1C1
*
(5.2 (1
:
Liebeskind, L.S. ; Welker, M.E. Tetrahedron Lett, ( 1 9841,
1)
73%
11 . 6 )
66%
3, 4341
* 91 % Chong, J.M.: Sharpless, K.B. Tetrahedron -Lett, (19851, 26, 4683
294 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Lo3:h
1 . KN(TMS)2,
Me
SECTION 314
TMSCl
2 . CH2N2
0
3.
L 5 i
KOH,
4. H2,
Pd-C,
"o Vi'% z c ~Me oH
t
MeOH MeOH
82% (2S,3R
1 . PhCHO, CsF,
HO
THF
reflux
C H 3 C H C 0 2 S i M e 3 o____L__)p
I
SiMe3
h
v
z
HO H ph/\/'OzH
Me
2 . H30t
(74
-
I
C H C H CCH2C02Me 3 21 Me
PLE 1M p h o s p h a t e
(2)
t
ke 26)
:
Bellasoued, M.; D u b o i s , J.-E.; Bertounesque, E. Tetrahedron Lett, (1986), OH
2,1152
J Org C h m , (1986),
Y
Kallmerten, J . ; GoUld, T . J .
= major)
84%
3, 2623 OH I
C H 3 C H 2 1CCH2COOH Me 51 %
(2)
3d
PLE = P i g L i v e r E s t e r a s e
Wilsgn, W.K.; Baca, S.B.; Barber, Y.J.; Scallen, T . J . ; horrow, m
.
L.J.
--J Org Chere, (1983),
SECTION 314: Carboxylic
Acid -
Aldehyde
No Additional Examples
48,
3960
ACID
SECTION 31 5
SECTION 315: Carboxylic
-
Acid -
295
AMIDE
Amide
c::-
1 . ~ B U O ~ C N) E~t 3 ~ ,
sd
DMAP, 25"C, 8 h
Flynn, D.L.;
H
t 2 . 3 L i O H , a q . THF RT * Zelle, R . E . ; Grieco, P.A. J Org Chem, (1983), 48, 2424
B 0C
96%
-
-
1 . 3 BnO2CNH2, 6 N E t 3 3 NCS, MeOH, 0 ° C 2 . 0 3 , CH2C12/MeOH, - 7 8 ° C
tt0I
3 . Me2S, - 7 8
Me
-
NH-CBZ 40%
25°C
4 . Cr03, a q . H2S04
(79% ee) acetone Fitzner, J.N.; Shea, R . G . ; Fankhauser, J . E . ; Hopkins, P.B. -J Org Chem, (19851, 50, 419 m\ l \- N a t , 2.
L)NCPh,
1
P h2CH COOH
-15"C-RT,
3. HS
Stamm, H. 0
* : Weiss,
0
" A0 BnC-N
U
B n +''
Evans, D.A.
R.
THF Id
*
Ph
I
PhCNHCH CH CCOOH
21
Ph
58 %
Synthesis, (19861, 395
1 . L D A , THF, - 7 8 ° C 2. B O C - N = N - B O C
Bn-CH-COOH I
t
3 . g l . AcOH
4 . L - i O H , a q . THF
* ; Britton,
19
T.C.;
*
N-BOC I
NH-BOC
(99% ee)
Dorow, R . L . ;
7 5%
Dellaria, J . F . 6395
J Am Chem Soc, (19861, ----
108,
296 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. nBuLi
0
2.
Bn-CH-COOH
Id
PhCCl
I
Trimble, L.A.;
y-BOC NH-BOC
*
3 . LDA i -Pr
SECTION 316
4 . BOC-N=N-BOC 85% 5. LiSH (R:S = 17:83) 6 . AcOOH * Vederas, J . C . ---J Am Chan Soc, (1986),
108,6397
Related Methods: Acid-mine (Section 31 6) hide-Ester (Section 344) mine-Ester (Section 351
SECTION 316: Carboxylic Acid - Amine 1 . BnNH2,
4A s i e v e
2 . TMS-CN,
CH2C12
C H 3 C H = C H C H 0 3 . 6N H C 1 ,
reflux
4.
Greenlee, W.J.
COOH
I
*
CH 3CH = C H C H NHB n
Dowex 50W-X4 HOHIPyIMeOH
43%
J Or& Chan, (19841, 49, 2632
-
)I
1 . EtOH,
H2NT:
Me2NH,
2 . LBuCHO,
3. PhC02)0, 4.
CH3
LDA,
RT
pentane
THF,
30°C -78
B r CH e
COOH
- 0 ° C *cH3+NH2 O
M
e
62
OMe HO \ / 6N H C 1 , 1 8 5 ° C Dowex 50W-X8(Ht) HO 43% )t Seebach, D. ; Aebi, J . D . ; Naef, I?.; Weber, T. Helv Chim Acta, (1985), 144 5. 6.
---
68,
C02Et
Ph2C=N
OA c
O'Connell,
P h - B a
,
tBu
1
2.
HC1-Et20
3.
6M H C 1 ,
* M.J. ; Falmagne,
297
AMINE
d : ' K t ,
1.
\
-
ACID
SECTION 31 6
THF,
0°C
31%
JCS Chem Comn, (19851, 1168
J.-B.
2. MeI,
( MeS ) 2 C = N C H 2 ! - N 3
3/
< OMOM
1
PhCHCOOH
heat
1 . LDA. THF.
,OMOM
o d
NH 2
*
-78
-78°C
-
1 N HC1
Me
-20°C
*
\
H2NCHCOOH 82%
*
(95% eel Ikegami, S.; Hayama, T . ; Katsuki, T. ; Yamaguchi, M.
-
Tetrahedron Lett, (19861,
e x c e s s Et2NH
P
O
O
H
RT,
Chow, J.M.; Sharpless, K.B.
02CCH=CHMe
OOH
4h
1.5 Ti(OiPr)4
.r\_C7H15
* -J org
OH NEt,
(20
1.
EtCU.BF3
2.
LDA,
3.
NaN3
4.
Ti(OBn)4
,
1)
92%
50,
(19851,
TMSCl,
Et
5 . H2/Pd
Oppolzer, W.*;
3, 3403
1560
97.8% ee
99.3% ee 37%
Pedrosa, R . ; Moretti, R.
Tetrahedron E ,(1986),
3, 831
298 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . NBS, P
h
d
CBZ
CC14,
reflux
2 . CH2=C: O E t OSiMe2tBu
4
o
ZnC12,
+
*
THF
3 .HOH
4.
H2/PdC12,
,
20 psi
SECTION 316
3
XHO 2 CH 2 C 0 2 E t
EtOH 25°C
71 %
(97% ee)
*
Sinclair, P.J.; Zhai, D.: Reibenspies, J.: killiams, R.M. 108, 1103 J Am Chem Soc, (1986), ---1. PhCHO
(TMS)2NCH=C(OTMS)2 Me3SiOTf,
2. H30
-78"C,
H ; 2
3h
t
t
PhCHCHCOOH I
OH
95%
(threo:erythro
= 2 : l )
*
Hvidt, T.; Martin, O.R.; Szarek, W.A. Tetrahedron Lett, ( 1 986),
3, 3807
1 . BOC-N=N-BOC
phro H J
TiC14,
CH2C12,
2 . CF3COOH,
Me&NMe, OTMS H
3.
LiOH
4.
D o w e x 50W
5. H2/Pt02
6.
Gennari, C.
* : Colombo,
D o w e x 50W
-78°C
RT 50% (98% ee R)
L.: Bertolini, G. J Am Chem Soc, (19861, 108, 6394 ----
SECTION 317
ACID
-
ESTER
299
1 . [Au(Cy-NC),]+BF4-
c a t . , Me02CCH2NC
PhCHO
2 . c o n c . HCl/MeOH,
50°C
3 . 6 N HC1, 8 0 ° C , 6h cat. =
t
90%
@ + NPPh, 5Ntt2
PPh,
Ito,
HO *COOH Ph NH,*HCI
* Y. ; Sawamura, M.;
*
Hayashi, T. J Am Chem Soc, (19861, ----
108,6405
Related Methods: Acid-hide (Section 31 5) hide-Ester (Section 344) Amine-Ester (Section 351
-
SETION 317: Carboxylic Acid * Ester COOH
NaN02/aq. H2S04 t
R T , 15h 70%
Gringore, O.H.;
Rouessac, F.P.
63,121
Org Syn, (19841,
NaIO4-RuO4.2H20 CC1 4 - H O H , 1 Oh
nB u
*
t
Torii, S. ; Inokuchi, T.; Kondo, K. --J Org Chem, (19851,
nBu
93%
50,
4980
300 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 318
C02Me
+
CCOOH
CH2N2
quant.
* Ogawa, H.; Chihara, T.; Taya, K.
---J Am Chem Soc,
PLE,
nBu$,C02Me
C02Fle
pH 8 ,
0.1N
(19851,
107, 1365
NaOH t n B u T. C02H
phosphate
C02Me
( R-: S- = 2 5 : 7 5 ) PLE = P i g * L i v e r E s t e r a s e Schneider, M. ; Engel, N.; Boensmann, H. Angw Chem Int Ed h g l , (19841, 23, 66 CH2C02Me CH2C02Me
PLE, aq.
pH 7
*
KH2P04
H-7,
CH2C02Me
( 7 9 ~e e
PLE = P i g L i v e r E s t e r a s e
CH,COOH
* Jones, J.B.
~f
95%
Lam, L.K.P.; Hui, R.A.H.F.; -J Org Chem, (1986), .-51, 2047 SECTION
- Ether,
318: Carboxylic
Epoxide, Thioether
1 . Na2W04.2H20, n P r C H =CHCOOH
HOH, 2 . aq.
1N K O H ,
3h
0 65OC / \ t nPrCH-CHCOOH
PH 6 H202(pH 5.8-6.8)
*
Kirshenbaum, K.S.; Sharpless, K.B. -J Org Chem, (19851,
50,
82%
1979
SECTION 319
ACID
-
HALIDE
1 . NaHC03, a q . a c e t o n e
2 . K H S 0 5 , Na2EDTA
PhCH=CHCOOH
>
27"C, 2h 3 . a q . HCI
*
Corey, P.F. ; Ward, F.E.
PhCH-CHCOOH 92%
-J Org
Chem, (1986),
1 . 2 L D A , THF/HMPA -78OC
PhCH2COOH
0
/ \
2 . BrCH2SeBn, l h -78OC RT
51, 1925 CH2SeBn
>
I
PhCHCOOH
-
81 %
* Reich, H.J. ; Jasperse, C.P.; Renga, J.M. -J Org e, (19861, 2,2981 SECTION 319: Carboxylic Acid
- Halide, Sulfonate
C 1 2 , C1S03H
C H 3 ( C H 2 l 1 6COOH
TCNQ, 15OOC
*
c1
I
CH3(CH2)1 5CHCOOH 88%
TCNQ = 7 , 7 , 8 , 8 - t e t r a c y a n o q u i n o d i r n e t h a n e
Crawford, R.J.
* -J Org Chem,
(1983),
48,
1364
1 . M e M g I , THF
ref1 ux
H C Z C C 0OH
2 . AcOH
*
>
ICH=CHCOOH
(I)
80%
Jung, M.E. ; Hagenak, J.A.: Long-Mei, Z. Tetrahedron -.Lett, (19831,
2, 3973
302 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Br
NaN02, K B r i PrCHCOOH
SECTION 320
>
H F/ PY
I
iPrCHCOOH 84%
Shih, J.; Surya Prakash, G.K. Helv Chim Acta, (19831,
Olah, G.A.;
---
12,
CH3COOH
CU(OAC)~
>
r e f l u x , 40h
Horiuchi, C.A.
* : Satoh,
1028
ICH2COOH 80%
-Chem Lett,
J.Y.
66,
(19841, 1509 Br
0
It
1 . LiA1H4
P h 2 A s CH C O O H
I
nBu -
2. Br2
* T. ; Joussen,
KauffmaM,
t
I
nBuCHCOOH
56% R.; Woltermann, A. Chem Ber, (1986), 119,2135
7 -
SECTION 320: Carboxylic Acid
-
Ketone 0 II
S
1 . PhCCH,,
K
3
BrHgO2CNUN
150°C
COZMgBr 2 . H30
4 eq.
*
DMSO
0
II
PhCCH2COOH
t
74%
*
Matsumura, N . ; Asai, N.; Yoneda, S. JCS Qleol Cam, (1983), 1487
---
SECTION 320
ACID
-
303
KETONE
H O H / MeOH Me0
Kunz,
COOH
* H. ; Lindig,
I1
*
PhCCH2CH2COOH
7OoC, 3 0 m i n
Chem Ber, (1983),
M.
1 . 2 LDA, THF, 2 . HMPT,
CH3(CH2)4COOH
0
RT,
-
116,220
-50°C nBu
It -1
*
CH3CCH2CHCOOH
0°C
65%
4 . a q . H C 1 , RT,
overnight
Miyashita, M.; Yamaguchi, R. ; Yoshikoshi, A. J Org C h a , (1984),
-
0
30 m i n
3 . CH2=CMeN02, 4 h
-100
quant.
-
*
2, 2857
0 II
OSiMe,
1 . MeCH-CHCCN, CH2C12,
-70
TiC14
-
-30°C
*
2 . HOH
65%
El-Abed, D.; Jellal, A.; Santelli, M. Tetrahedron 0
II
PhCH=CHCCH3
e
-
,
C02,
*
E, ( 1 984), 25, 4503
MeCN
COOH 0
w-
I
II
PhCHCH 2 C C H
Hg e l e c t r o d e s Et4NtC104-
* A . ; Sasaki, K.
Harada, J.; Sakakibara, Y.; Kunai, Bull chem Soc
--- e, (19841,
82%
57,
611
304 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 320
0
l o 2 , MeOH, 4 0 ° C h 7
Rose B e n g a l ,
4h 91 %
Utaka, M.;
*
Nakatani, M . ; Takeda, A. Tetrahedron, (19851,
C02TMS
1. LiBr,
I
2 . PhCC1,
:
CH2
I
C02TMS
Et20, O"C,
NEt3
0
it
l h
3 . a q . NaHC03
4.
2, 2163
*
PhCCH2COOH
88%
4M H 2 S 0 4 ( p H 2 - 3 )
Rathke, M.W."; Nowak, M.A.
-Syn Conmun,
(1985), 15, 1039
Br
I
PhCHCH3
C O ~ ( C O ) ~ ,C a ( O H ) 2 tBuOH,
1 atm. CO 25"C, HOH
t
PhCHCCOOH
J
CH3
72% \
Francalanci, F.; Bencini, E.; Gardano, A.: Vincenti, M.: Foa, M. Chem, ( 1 9861, 301, c027 -J Organomet Review: lISynthesis and Properties of a-Keto-Acidsl1
Cooper, A.J.L.;
Ginos, J . Z . ; Meister, A. Chem Rev, (19831, 83, 321 --
Also via: Ketoesters (Section 360)
SECTION 322
ACID
SECTION 321: Carboxylic Acid
-
-
OLEFIN
-
Nitrile
305
1. nBuLi 2 . Me1 3. EBuLi
4. E t I 5 . 6 n HC1
'OMOM
6.
Me E t
m
xC02H CN 65%
1 % K C03/MeOH
(R) Hanamoto, T.; Katsuki, T. ; l/?amaguchi,M. Tetrahedron Lett, (1986), 27, 2463 Also
via: Cyanoesters (Section 361
-.SECTION
322: Carboxylic Acid
-
Olefin
MeOH
* Saito, I. ; Nagata, R.;
49%
Yuba, K.; Matsuura, T.
Tetrahedron Lett, (1983),
0
1 . LiN(TMS)*,
II
OCEt
2, 1737,
THF
-78°C 2 . t B u M e 2 S iC1
HMPA, 36
Ireland, R.E. ; Varney, M.D.
4439
Me
HozC-
>
-78°C-RT
2 Am
I
S i-LB u \
Me
93%
chem SOC, (1984),
106,3668
306 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 322
0
II
1 . CH2=CHCSiMe3,
SiMe,
TiC14
CH2C1 2 , - 7 8 ° C 2 . a q . NaOH, THF,
aq.
30% H202
-40°C
49%
Danheiser, R.L.*; Fink, D.M.
26,
Tetrahedron E ,(1985), 1.
0
,
TiC14
2 . L i O H , T H F , HOH
0
2509, 251 3
""'COOH (99.9% ee)
* Helmchen, G.
*D,, , d,,
Poll, T.: Sobczak, A.; Hartmann, H.: Tetrahedron E ,(19851,
a:::";.. MeMgBr,
THF
79%
26, 3095
+
"I'
'I,,
C u B r -Sli;'e2
COOH
OH 2) 97%
-20°C ( 98 * Curran, D.P. ; Chen, M.-H.; Leszczweski, D.; Elliott, R.L.; Rakiewicz, D.M. J Org &em, (19861, 51, 1612 P Ph3
\ /
co
I.
CH2=CH C
II 0
*
, znc12
CH2C12,
Fe
/ \
Q
RT b 7
CP
2.
Davies, S.G. ; Walker, J.C.
CAN,
a q . THF
COOH
( 2t
= major)
JCS Chem Conm, (19861, 609
80%
SECTION 323
ALCOHOL
-
307
ALCOHOL
Also via: Hydroxy acids (Section 313); Olefinic amides (Section
349); Olefinic esters (Section 362); Olefinic nitriles (Section 376).
SECTION 323: A l ~ h o l ,-.Thiol
-
1 . 2 Sm12, PhCHO
2 . H,O
-
-
Alcohols Thiol
OH
0.5 min
I
t
t
PhCHCH Ph
I
*
J
OH
Namy, J.L.:
Souppe, J.; Kagan, H.B. Tetrahedron Lett, (1983), 24, 765
4
Zn ( B H 4 ) 2 &Bu U P
-
B
0
Et20,
*
0°C
*
+ 4
-
B
95%
.
HO
HO (87
:
1 3 ) no y i e l d
Nakata, T. ; Tanaka, T.; Oishi, T. Tetrahedron E ,(19831, 2, 2653
*
Me N H + B ( O A C ) ~ - , AcOH
R -
Me?N, - 2 O o C , 5 h 8 6 % ( a n t i : s m = 96:4) * D.A. : Chapman, K.T. Tetrahedron E,(19861, 3, 5939
iPr
Evans,
FR
R = Ph
1. Dibal-H,
*
2.
THF
1 0 % HC1
87%
(un:anti
=
93:7)
Kiyooka, S. ; Kuroda, H.; Shimasaki, Y. Tetrahedron Lett, (1986), 3, 3009
R
= Me
Anwar, S.;
1 . iPr2SiHC1,
Py,
PhH
2 . SnC14, CH2C12, - 8 0 ° C 61 % 3 . a q s HF, MeCN Davis, A.P. JCS Chem Corn, (19861, 831
308 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
u"
Ph Br
O*Si /J
/ \
Nishiyama,
1 . nBu3SnH, AIBN PhH, reflux
---n + APh /Ph
*
2 . 30% H202, K F D M F , 6 0 " C , 8h
* H. ; Katajima,
SECTION 323
HO OH (84
HO
OH
16)
85%
T.; Matsumoto, M.; Itoh, K. (19841, 9, 2298
J Org Chat, ---
a
1. nBuLi 2'
3. E t C B n
'd
Li
, THF, -78°C
Et
b r
* D.
(SR:SS
Nijera, C.; Yus, M.; Seebach, Helv Chim Acta, (1984), ---
55% = 1:l)
3, 289
( e r y t h r o : t h r e o = 4:l) * Pelter, A. ; Bugden, G.: Rosser, R. Tetrahedmn Lett, (1985), 26, 5097
SECTION 323
ALCOHOL
ALCOHOL
a na p i
309
PhCH =CH Ph
(E)
-
-1
O O O C
%,,,A
t
Ph
( 9 0 % ee R R )
Chem Lett, (19861, 131
Yamada, T.; Narasaka, K .
,wN Me
Os04,
Tokles, M.; Snyder, J . K .
0
OH
t-8"
Collum, D.B.:
*
0
( 8 6 % ee R )
Tetrahedron E ,(19861,
II
RT, 1 2 h
2 . L i A 1 H 4 , THF,
75%
3, 3957 Ye
,+"
O°C
3 . HOH
*
I
t -B"
OH
58%
(inversi0n:retention = 8:l)
Still, W.C.;
*
Mohamadi, F. J Am Chem Soc, (19861, ---RT,
l h
108,2094 A
2 . H2PtC16*6H20 6OoC, 1 0 m i n )
3 . 3 0 % H 2 0 2 , NaHC03
* Tgao, K. ; Tanaka, T.; Nakajima, T.; 1.
OH
"'0
1 . H g ( O C C F 3 ) 2 , CH2C12
no"
I,
%, 1
CH3(CH2)4-C-CH20H
RT
1 . TMS2NH,
-
H
QNMe:
CH,(CH,),CH=CH~
OH 71 %
O
H
69%
Sumiya, R.; Arai, H.; Ito,
Tetrahedron E ,(19861, 3, 3377 * Tamao, 4 . ; Nakajima, T.; Sumiya, R.; Arai, H.; Higuchi, N.; Ito, Y." Am -.Chem Soc, (19861, 108,6090 -J -
310 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 324
Review: "Stereoselective Reduction of B-Hydroxy Ketones
to 1 ,3-Diolsff
*
Tetrahedron, (19841, 40, 2233
Narasaka, K. ; Pai, F.-C.
&
Also
&
via: Hydroxyesters (Section 327); Diesters (Section 357)
SECTION 324: Alcohol, Thiol ---
Aldehyde
1. ~C u1 COHH2 /SL0 B2 PuhO K
0
THF,
10°C
Ho
-e
2 . tBuOH/tBuOK t-BuO TH F
t-BuO
t r . HOH,
64%
25,"C
: Christy, M.R.: (1984), 49, 1378
Adamczyk, M.; Dolence, E.K.: Watt, D.S. Reibenspies, J.H.; Anderson, O.P.
--J Org Chem,
0
To 1
iii'"',s\
"
*.
11NMe2
1
.
2.
tBuLi,
HMPA/THF
-78"C,
3 0 rnin
PhCHO,
20°C
3 . Na/Hg 4. A n n u n z i a t a , R . ; Cozzi, F.; C i n q u i n i , C . ; P o l l , G . ; S c o l a s t i c o , C.
6
M.
*
JCS Perkin I, ---
1 . CN 1a HC ,H 2 SDMSO 02CH2C1 2. TiC104,
HOH
PH i
*
PhCHCH2CH
40%
; Colombo,
(34% e e ) L.; G e n n a r i ,
dCH
(1 9851, 251
*
Nagashima, E.: Suzuki, K.; Ishikawa, M.: Sekiya, M. Heterocycles, (19851,
t
32%
23, 1873
SECTION 325
ALCOHOL
-
AMIDE
OH
I
CH3CHCH2CH20H
Cp2ZrH2,
Nakano, T.; Terada, T.:
150°C,
8h
OH
I
*
CH3CHCH2CH0 98%
Ishi, Y. ; Ogawa, M. Synthesis, (19861, 774 it
Related Methods: AlcoholaKetone (Section 330) SECTION
325: Alcohol, Thiol - Amide 0
i
1 . LBuMgBr,
i
To1
0
OH
-78OC
/ S Y" H ~ C N M ~ ~ *.
THF
I
I1
iPrCHCH2CNMe2
2 . iPrCH2CH0 3 . Na/Hg
73% (89% ee S )
Annunziata, R.; Cinquini, M.; Cozzi, F.; Montanari, F.: A. --JCS C h a n Cam, (19831, 1138 PhMe2SiH, CF3COOH
( 9 9 % e r y t h r o ) Me
*
O O C ,
DMPU
YNE
Ph v N E t 2 9 8 %
O°C
phQNEt2 Me PhMe2SiH,
P e s t e l 1i
TASF
Ph
(99% threo)
Me
TASF = t r i s ( d i e t h y 1 a m i n o ) s u l f o n i u m d i f l u o r o t r i m e t h y l silicate DMPU = 1 , 3 7 d ~ m e t h y l - 3 , 4 , 5 , 6 - t e t r a h y d r o - 2 ( 1 H ) g y r 1 m 1 d 1 no n ey 2 Am chem SOC, (1985), 107, 8294 Fujita, , Hiyama, T.
.
98%
312 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0
0
I
*
RCFHCNR'R'
Me
1 . Zn(BH4)2, E t 2 0 , -78°C 2 . 3% a q . H2P04 (vn:anti
R = Me, R 1 = H R 2 = BR
Ito, Y.; Yamaguchi, : :
II
R C H IC H C N R ~R~
Me
R
0
OH
II
II
SECTION 325
iPr,
R1
* M.
Tetmhecjmn E ,(19831,
= Me
KBEt3H,
R 2 = CH2CH20SiMe2tBu
Ito, Y.; Katsuki, T.;
* Yamaguchi, M.
= 97:3)
2,5385
Et20
0°C
97%
95% ( w : a n t i
-
Tetrahedron Lett, (19851,
26,
= 1:80)
4643
NMe CH3(CH2)4CH0
, ooc
1 .C13Ti-C-C1 2 . 2N HC1,
Schiess, M.; Seebach, D.
0
*
CH3(CH
RT
Ph
E t O C N C l Na
, AgN03
1 % Os04,
MeCN, RT
HPh NH C02Et
min 69% * 5Org s, (19831, 61,93
HOH,
Herranz, E.; Sharpless, K.B. OSiMe2tBu
&Ao \ O S iMe 2 t B u
0s i M e 2 t B u
1 . CBuLi 2 . Cp2ZrC12
3 . DMAP
4.
*
&iKh '0s
PhCHO
Katsuki, T.; Yamaguchi,
* M.
OH
>
PhCH=CHPh
(g
96%
(19831, 6 6 , 1618
0 II
) CHCNHMe
2 41
OH
Helv Chim Acta, ---
II
(R:?
iMe2tBu
= 4.4:l)
-
94%
Tetrahedral? Lett, (19851, 26, 5807
SECTION 326
-
ALCOHOL
31 3
AMINE
1. nBu2BOS02Me V
O
CH2C12,
("K//'
2.
EtCHO,
3. aq.
-78OC
-78OC
L/
0
OH
t
NaHS04
4. H202,
Evans, D.A.*;
NEt3,
pH 7
94%
Sjogren, E.B.; Bartroli, J.; DOW, R+L. Tetrahedron Lett, (1 9861, 3, 4957 1 . C H 23 CN1= 2C ,= 0 ,P h C BH C 31 3
reflux.
*
12h
* 2 . 5 % H C 1 , RT, 2 h Pigcolo, 0. ; Filippini, L.; Tinucci, L.;
A.
&!NHMe Me0
75%
Valoti, E.; Citterio,
Tetrahedron, (19861,
9, 885
1. n B u L i , THF
4
0
Et
OMOM
-1 00°C HO
2. Cp2ZrC12 -100 - - 7 o o c 3 . a q . KF 4 . + S i 0 2
MO M0
(92% de)
75%
Uchikawa, M.; Hanamoto, T.: Katsuki, T. ; Yamaguchi, M. Tetrahedron Lett, (1 9861, 3, 4577 4581 Amine -- -
SECTION 326: Alcohol, Thiol
-
S
/ \
CH3CH-CH
Taddei, M.:
1
.
M e 3 S n N E t 2 , CH2C1 reflux Id
2 . H02CCH2C02H, 1 . 5 mmHg
1 5OoC
SH
>
I
CH3CHCH2NEt2
Papini, A , ; Fiorenza, M.; Ricci, A . Tetrahedron ( 1 9831,
s,
55%
24,
231 1
314 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
'3-0 ,
DCE
ts
TFA,
reflux,
*
I d
@OH
64% Tetrahedron E,(1983), 2, 3051
SiMe, CO,Me
Chan, T.H.;
SECTION 326
Kang, G.J.
1 . MeOH/HOH, r e f l u x 2. A m b e r l y s t A26 MeOH , R T - r e f 1 u x
O y N 3.
CCI,
6F1 HC1
HO t
e H ; : , + -
OH
86%
*
C a r d i l l o , G. ; Orena, M.:
Sandri, S. JCS Chem -.Carm, (19831, 1489
--
1 . TsNCl -Nat .3H20
1 % Os04, 60°C, 2.
Herranz, E.;
CHC13/HOH
BnNEt3C1
Na2S03,
81%
reflux
* Sharpless, K.B.
Org Syn, (1983),
2 CH2=CHCH=CH2, Pd(acac)2,
t
0.5
80°C PPh3
* ~C5Hll
autoclave
Groult, A . : Guy, A .
61,85
Tetrahedron, (19831,
98%
2,1543
NH
ALCOHOL
SECTION 326
/ 0 \
-
AMINE
,
1. Me3Sn-N3
PhCH-CH2
reflux, 2,
Fiorenza, M.;
CH2C12
*
16h
Ph&OH
H02CCH C 0 2 H , E t 2 0 r e f l u x , 2h Ricci, A. ; Taddei, M.; Tassi, D. Synthesis, (1 9831, 640
*
r e f 1ux
*
315
2.
83%
(96
LiA1H(OMe)3, NaOMe, E t 2 0
92%
O°C
4)
Narasaka, K. ; Ukaji, Y . ; Yamazaki, S. Bull Chem Soc J , (19861, 59, 525 --* Chem Ftt, ($41, 147 Narasaka, K . ; Ukaji, Y . Narasaka, K . ; Yamazaki, S.; Ukaji, Y . Chem Lett, (19841, 2065
Jacquesy, J.-C.; Jouannetaud, M.-P.;
Tetrahedron
0 A,NMe* Ph A Me
Morellet, G.; Vidal, Y .
E,(19841, 25, 1479 HO
PhMe2SiH, TBAF,
>
phOyNMe* Me 8 3 %
HMPA 12h
Fujita, M . ; Hiyama, T.
RT
* -J Am .-Chem Soc,
(threo:erythro
(19841,
106, 4629
= 99:l)
316 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CH2=C
/
1 . Ph-NZO,
OTMS
PhH
2O0C
*
SECTION 326
OH
I
PhCHCH2NHPh
2. LiA1H4, E t 2 0 78% * Sasaki, T.; Mori, K.; Ohno, M. Synthesis, (19851, 280 h
P‘
0 EtCH-CHCH20H / \
e x c e s s Et2NH RT, 5 h _______)
1 .5 T i ( O i P r ) 4
*
Caron, M. ; Sharpless, K.B.
OH NEt
E t A . p c 3 I - l
OH
Et+OH
+
NEt,
1 )
(20
90%
J Org Chm, (19851,
3, 1557 ~-Bu
0
Overman, L.E.
*
; Lesuisse, D. Tetrahedron Lett, (1985), 1 . TMS-CN, Zn12,
C H ,LC l , 12h
2 . HCl/MeOH 3 . N a O H , HOH
Cassman,
* P.G. ; Haberman,
L
*
91 %
26,
4167
c:* 61 %
L.M. Tetrahedron Lett, (19851,
-
26,
4971
SECTION 326
-
ALCOHOL
317
AMINE
HO Ph
1 . PhMgBr, Et20
CN I
CH3COSiMe3
RT
CH3
2 . NaBH4, MeOH RT
I
*
I 1
CH C -CHNH
rn
I
CH3
*
84 1
Krepski, L.R. ; Jensen, K.M.; Heilmann, S.M. ; Rasmussen, J.K. synthesis, (19861, 301 NHTMS / 0\
PhbHCH3
Ph CH- CH
(R)
(2),
65OC
H OHH
2-y;
>
Ph
H
44h
80%
*
Atkins, R.K.; Frazier, J.; Moore, L.L.; Weigel, L.O. Tetrahedron Lett, (19861, 3,2451
4
SiMe,
n B u N H 2 * T F A , 35°C HOH,
48h
37% aq. HCHO
Larsen, S.D.; Grieco, P.A.*; Fobare, W.F. ---J Am Chem Soc, (19861, 1 . (-) I
IpC2BH, -15OC
2 . NaOH/HOH
t I
Bn
Bn
IpC2BH = i s o p i n o c a m p h e n y l b o r a n e
Brown, H.C.
108,3512
* ; Prasad,
94%
(84% e e )
J.V.N.V.; Gupta, A.K. -J Org Chem, (19861,
51,
4296
89%
318 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION
RU
327: Alcd.lol,
O
R
"hi01
-
Ester
'
*
R = CH2CH=CMe2 R ' = Me'
R
O R'
M
Baker's Yeast, MgS04 D-glucose, KH2P04, H O H
*
*
SECTION 327
7 3%
(92% ee)
Hirama, M. ; Shimizu, M.; Iwashita, M. JCS Chem Coma, (19831, 599 Thermoanaerobium brockii R = Et 80% Trypton, Na2S, y e a s t extract R' = E t (84% ee S ) D-g1 u c o s e * Seebach, D. ; Ziisr, M.F.: Giovannini, F.; Sonnleitner, B.: Fieehter, A. ,mewChem Int Ed R q l , (19841, 23, 151 R = Me Baker's Yeast, HOH E' = Et s u c r o s e , 30°C (S:! = 93:7) -7-
*
Seebach, D. ; Sutler, M.A.; Weber, R.H.; Ziiger, M.F. Org Syn, (19841, 63, 1 Seebach, D * ; Giovannini , F ; Lamatsch, B. Helv Chim Acta, (1985), 68, 958
.
.
---
LiBH4, L B u O H , THF 94% (RR')NN'dibenzoyl (87% ee R) * cystine, -78 - - 3 O O C Soai, K. ; Yamanoi, T.; Hikima, H.: Oyamada, H. JCS Chem Coma, (1985), 138 ---
R = Ph R' = Et
*
0
V-Sn
Bu,
H CIIC 0 2 B u
, w oMe2 B u
CH,C1
HO (80
L
*
L
,&CO,Bu Me
+ 20)
90%
Yamamoto, Y. ; Maeda, N.; Maruyama, K. JCS Chem Coma, (1983), 774 7 -
SECTION 327
-
ALCOHOL
BrCH2C02Et,
ESTER
0°C
319
c O,Et
>
Z n - g r a p h it e
Boldrini, G.P.; gavoia, D.; Tagliavini, E.; Trombini, C.*; Umani-Ronchi, A. -J Org Chem, (1983), 48, 4108
coi
P h C H 2CH 2 C H 0
OH
P ,r 0 - 2 o o c
C1 3Ti'
88%
I
BnCH2CHCH2CH2C02iPr
C H 2 C 1 2 , 2h 80% * J Am Chem Soc, (19831, 105, 651 Nakamura, E.; Kuwajima, I. ----
,0SiMe2tBu
Me
PhXCHO
2 . 8 C H = C 'OMe
Me
* Ph*CO,Me
t Ph&C02Me
OH
CH2C12, B F 3 * 0 E t 2 HO -78"C, 4h (15 : 1) * 81 % Heathcock, C.H. ; Flippin, L.A. J Am Chem Soc, (19831, 105, 1667 ----
THF,
-78°C
( 9 2 % ee S )
X:&070 K+
G i # O
80%
O&
H * Brown, H.C. ; Cho, B.T.: Park, W.S.
--J Org
= K9-DIPGF9-BBNH
Chem, (1986), 51, 3396
320 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
a v 0
0
II
>
CH,
PhCC02Et
SnCl 2 / D i b a l -H,
Mukaiyama,
T.;
-1
C H 30 IIC C 0 2 E t
G.G.;
(19851, 813, 1359
0
OH
I
CH3CHC02Et 81 %
( 8 9 % ee S ) Jadhav, P - K . J Am cfe im Soc, (1984), 1531 ----
106,
OH
S iMe3
I
TBAF
D(
C02Me
C02Me
* ; Blankenship,
Wells, G.J. J Am Chem Soc, (19841, ----
1 . L I C A , THF -8OOC
II
R*OCCH3
R*
[XCHCH3
>
CH 3CH0
Paquette, L.A.
0
90%
24h
O O C ,
* ; Pai,
*
(85% ee S )
P
-Chem Lett,
OH PhtHCO2Et
O O O C
20 rnin Tomimori, K . ; Oriyama, T.
o ,
Brown, H.C.
CH2C12
SECTION 327
106,6442
RO-Et
9
F
3.
*
90%
+
+H!:ri z
C.;
HO
0 (93
:
EtCHO, TiC14 CH2C1
- Ar
HO 7) 67%
A r :I@
I
Helrnchen , G. ; Lei kauf , U. ; Taufer-Knbpf e l , I. Angew C h a Int Ed Engl, (1985),
---
2, 874
ALCOHOL - E S T E R
SECTION 327
n Ho
0
OH
CH2C12, N E t 3 ,
*
K i m , S . ; Chang, H.;
Wulff, W.D.
K i m , W.J.
Soc, (1985),
'd
Zr(acac)4y
I
CH3CH(CH2)40Ac
60h
Hirobe, M.
94%
*
Tetrahedron Lett, (1985) , 26, 1977
1 . CH2=C; -195
,SL i
-
2 . H30t
SEt
THF/Et20
-120°C
Ph
Me
Me
COSEt
OH (96
OH
50%
Meyers, A . I .
107, 503
OH
t
Kunieda, T. ; Mori, T.; Higuchi; T.;
PhCHCHO
HO
P N A c
I
*
o y P h 0 93% J Org Chem, (19851, 50, 1751 Id
J Am Chem ----
S.R.
CH2C1
CH3CH(CH2)40H
n
73%
* ; Gilbertson,
OH
t
321
* ; Walkup,
R.D.
Tetrahedron, (19851,
4);
2,5089
322 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 327
1. 2 LiNEt2
OH
I
THF/HMPA
CH3CH(CH2)3C02tB~
-100
-
Me
t
-78°C
2 . Me2S04
Me
- 1 00°C
-Chem Lett,
Narasaka, K . ; Ukaji, Y.
HO
HO OH wPr & c o p
P
0
(8)
71 %
(19861, 81
F e C 1 2 , MeOH
V&CO,Me
(92)
90%
50 p s i H2 18h
(9n:anti = 9:l)
*
Y
Kathawala, F.G.; Prager, B.; Prasad, K . ; Repic, 0.; Shapiro, M . J . ; Stabler, R.S.; Widler, L. Helv Chim Acta, (19861, 69, 803
---
qMS 0
C02Et
%,
TiCl
4 y
-78OC,
Molander, G.A.
* ; Andrews,
SCEt3
Masamune,
* S. ; Sato,
OH C02Et Me
CH2C1
I
> 2h 88%
S.W. Tetrahedron Lett, (19861,
-
3, 3115
82%
pentane
(91 .2% ee R ) -78OC, 6 h T.; K i m , B.M.; Wollmann, T.A. ---J Am Chem Soc, (19861, 8279
108,
-
ALCOHOL
SECTION 327
0
MoOPH,
R * O l C H 2 C H 2Ph
ESTER
323
0
4h
II
>
R*OCCHCH2Ph I
2 KN(TMS)2 8 CH3CH2yHCH3
v
OH
(R:S Gamboni, R.; Tamm, C.
HO 55,
/
H
c H -c' - c o
*
Tetrahedron .-Lett, (1986),
1 . CsSAc, ET
DMF
overnight
2 . 3% H C l / E t O H
= 1:99)
3, 3999
H
*
7 3%
1S H C-' - C 0
%L$
CH
Et
86%
( 9 2 % ee R)
Strijtveen, B.: Kellogg, R.M.
* -J Org Chem,
co *Et
(19861,
51, 3664
- 6.. C02Et
Sm12,
-98OC
TH F / E t O H
* Molander, G.A. ; LaBelle, B.E.: Hahn, G. -J Org Chem, ( 1 9861, 51, Also via: Hydroxyacids (Section 313)
68%
5259
324 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 328: Alcohol, ,Thiol
--
Me
-
Ether, Epoxide, Thioether
Me
CH =CHCH2TMS
B n - 0 *CHO
SECTION 328
_______)
CH2C1 2 , - 7 8 ° C SnCl
Heathcock,
(35
:
I
4
94%
* C.H. ; Kiyooka,
S.; Blumenkopf, T.A. J 3Chem, (19841, 49, 4214 Kiyooka, S.; Heathcock, CTH. Tetrahedron E ,(1983), 24, 4765
a -R PdC12, CuCl
DMF,
45OC, 02'
T i u s , M.A.
* ; Thurkauf',
HOH,
NaHP04
2.5h
66%
A.
-J Org Chem,
(1983),
48,
3839
tBuOOH, PhH, 6h
"
O
n
A 1 ( O i P r ) 3 , 25OC
*
Takai, K.; Oshima, K. ; Nozaki, H.
80% (E : Z- = 1 3 : 8 7 )
---B u l l Chein Soc Jpn,
(1983), 56, 3791
SECTION 328
ALCOHOL
-
ETHER
- q rh?
0
(A)
)\
Ph Ph
OH
HOdNH-Bn Hw,ti(#JH-Bn
9
0
325
LBUOOH
'h
Ph
(k) T i ( O i P r ) 4 , - 2 O O c Johnson, R.A.;
Lu, L.D.L.;
CH3(CH2)7CH=CHCH20H
(L)
Hanson, R.M.; H i l l , J.G.;
OH
96% e e
F i M , M.G.; Sharpless, K.B. -J w g C h a p .(1984), 728
2,
( + I d ie t hyl t a r t r a t e
*
4 i sieve, - 2 0 0 ~
C H C1
OH
2.4:2
=
*
1 :2.0) 82% e e
0 nC8H17CH-CHCH20H / \
7 9%
-
-
Sharpless, K.g.* 30rFMChem, (1986), 51, 1922 Sharpless, K.B. ; Exon, : Regenye, R . Org S z , (19841, 63, 66
.
1 . BH2C1 - O E t 2 , E t E O lh O'C, 2. N a O H , H 2 0 2 EtOH
Borders, R . J . :
( C O )5Cr=C
,OMe
\
Wulff, W.D.
Bryson, T.A.
CECS iMe3
* : Yang,
1.
*
OTMS
'A
nPrC=CH,
, THF
~
50'C
OMe
2. Si02, a i r D.C.
90%
Chem L e t t , (1984), 9
----J Am Chem
58%
Soc,
(19841,
106,7565
326 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Sm12, T H F , RT
H?5°Bn
t
C1 C H 2 0 B n
*
SECTION 328
57%
Imamto, T. ; Takeyama, T.: Yokoyama, M.
ei 5,3225
Tetrahedron Lett, ( 1 9841,
6
Men
MeTiCl
Ma
CH2C1
Mori, A.; Maruoka, K.:
Yamamoto, H.
-
*
Me
,+"
H
(R:S
=
HO
4:96)
Tetrahedron E,(19841,
0.5% P d ( P P h 3 ) 4 ,
THF
P h O H , 10 m i n Deardorff, D.R.
0 SiMe,
0 I
Lee,
* ; Myles,
3, 4421
82%
D.C.; MacFerrin, K.D. Tetrahedron E,(19851,
2 . TiC14
26, 5615 OH
1 . Me3SnCH2CH2CH(OMe)2
* T.V. ; Richardson,
quant.
OMe
64% K.A.
-
Tetrahedron Lett, ( 1 985) I
26,
3629
SECTION 328
ALCOHOL
b
CF3COOH,
0
Ph X
H
327
ETHER
NaBH4
+
P h C H 2 0 C H 2CH 2 0 H
20°C
THF,
Nutaitis, C.F.; Gribble, G.W.
-
83%
*
Org &ep -Proc I n t , (1985),
nBu2Sn0, RT -
0
PhCH-CH2
OMe
OH
I
5h
/ \
17,1 1
*
I
t
PhCHCH20Me
PhCHCH20H
s, (19851, 26, 3219
Otera, J. ; Yoshinaga, Y.; Hirakawa, K. Tetrahedron
1 . NCS,
,,,,t(CH2)3SPh
2. MeLi,
-80°C
CC14 THF
-
RT
*
@SPh
*
Harada, T.; Akiba, E.; Tsujimoto, K.; Oku, A . Tetrahedron E,(19851, 1 . PhCHO, S,
Ph
\
CH 3
1.5h CH2C12
-78°C
CH2C12,
2 . ZnBr2,
CH3CH=C
Et3SiH,
-78 3 . HOH
Takeda, T.* ; Tsuchida,
-
-4O"C,
4h
49%
26, 4483 S P h OH
1
t
1
CH3CHCHCHPh
I
CH3
77%
T.: Nakagawa, I.; Ogawa, S . : Fujiwara, T. Tetrahedron E ,(19851, 26, 5313
328 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
'02, iP r C H =CH iP r
(r) W.
hw,
Ti (OiPr)4,
TPP = t e t r a p h e n y l Adam,
TPP,
* : Griesbeck, OH
I
0°C
porphine A.:
(L)
Staab, E.
C-CHCHiPr
Me'
T e t r a h e d r m Lett, (1 9861,
60"C,
/ \
7 5%
(erythro:threo
n B u 2 S n 0 , LBuOOH
CH3CH=CHCHnC6H1
0
Me,
t
CH2C1
SECTION 328
3, 2839 OH
0
I
/ \
CH3CH-CHCHnC6H1
7 5%
6h
Kanemoto, S.: Nonaka, T.; Oshima, K.
(threo:erythro
* : Utimoto,
K. Tetrahedron E ,(19861,
= 4:6)
3,3387
c1 I
PhSCHCH3 PhCHO
,
P
L i I
C r C 1 2 , TMEDA, THF, 6 h
>
25°C
h OH (88
Me
A Ph+
+
OH 12)
96%
Nakatsukasa, S.; Takai, K.*:
Utimoto, K.
-
J Org Chem, (19861, 51, 5045
1. Ti(OiPr)4, C H =C
,CH \
3
-20°C
( + ) d i i s o p r o p y l t a r t r a t e HO Me cumene h y d r o p e r o x i d e P h S A o H
CH20H
3 i sieve
2.
quant.
P(OMe)3
3.PhSH,
KO, S.Y. ; Sharpless, K.B.
= 9:l)
(92% ee)
Ti(OiPr)4
* -J Org Chem,
(19861,
2,5413
SECTION 329
ALCOHOL
-
HALIDE
329
Reviews:
"Chelation or Non-chelation Control in Addition Reactions of Chiral a and 8-Alkoxy Carbonyl Compoundstf Reetz, M.T.
*
Angeu Chem Int Ed Engl, (19841,
23, 556
"Asymmetric Epoxidation of Allylic Alcohols: The Sharpless Reaction" Pfenniger, A.
*
Synthesis, (19861, 89
SECTION 329: Alcohol, mi01
-
, THF, 4 d
1.
0
Halide, Sulfonate
PhCCH2Br
Brown,
2 . NaOH,
OH
*
II
H202
I
PhCHCH 2 B r 95%
* H.C. ; Pai, G.G. J Org Chem,
(86% ee R)
(19831,
48,
1784 Me
Li2NiBr4, 25"C,
THF
18h
*
Dawe, R.D.: Molinski, T.F.: Turner, J . V . Tetrahedron Lett, ( 1 9841, 1 . T i C 1 4 , LBuOOH " C 7 H 1 5CH=CHCH20Me
(r)
Klunder, J.M.:
CHzC12, 2 . Na2S04, RT,
96%
25, 2061 CI
-78°C +OM€! E t 2 0 nC7H15 HO
*
l h
Caron, M.; Uchiyama, M.; Sharpless, K.B. J Org Chem, (19851, 2,912
*
92%
330 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
NaI,
CH3CN,
SECTION 329
O°C
tBuOCl
*
I
'
Kometani, T. : Watt, D.S.*; Ji, T.; Fitz, T.
-J Org Chem,
50,
(19851,
5384
30 m i n
Gassman, P.G.*;
97%
quant
O'Reilly, N.J. Tetrahedron E,(1985),
26,
0
I
5243 OH
L i B H 4 , LBuOH,
II
THF
PhCCH2C1
1
*
PhCHCH2C1 76%
/CH2SSCH 2' C H NH C P h PhCNHCH "
*
I
COOH
(2,:)
1
HOOC
6
( 7 2 % ee S)
Soai, K. ; Yamanoi, T.: Hikima, H. J Organmt Chem, (1985),
-
0 \I
TBADH,
EtC(CH2)3C1
NADP, a q .
TRISSHC1 , H O C H 2 C H 2 S H 37°C
TBADH = T h e r m o a n a e r o b i u m b r o c k i i a l c o h o l dehydrogenase
*
iPrOH
Keinan, E. ; Seth, K.K.; Lamed, R. J Am Chem
-_--
290,
c023
OH
I
*
EtCH(CH2)3C1
82% ( 9 9 % ee S )
Soc, (19861,
108,3474
SECTION 329
-
ALCOHOL
0
CH212' THF,
33 1
HALIDE
Sm
*
0°C
n = l
* Imamoto, T. ; Takeyama, T.;
81 %
Koto, H.
Tetrahedron E ,( 1 9861,
n = O
3, 3243 82%
Tabuchi, T. ; Inanaga, J. *; Yamagkuchi, M. Tetrahedron Lett, (19861, 3, 3891 1 . Li2CuC14,
THF
\\to
4.75 h
>
CI
QOH
2 . HOH
Ciaccio, J.A.: Addess, K . J . : CI
Bell, T.W.
98%
*
Tetrahedron E ,( 1 9861,
3, 3697
(0:p = 6 0 : 1 8 % )
*
Umemoto, T. ; Kawada, K . ; Tomita, K.
-
Tetrahedron Lett, (19861,
3, 4465
332 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 330: Alcohol, Thiol Bn - 0 Me&CHO H
Me,
,OTMS
H'
'Ph
c =c
TiC14,
SECTION 330
Ketone
-
0
HO +
Bn-0
Me (97
-78OC
Me
BnO
3)
:
no y i e l d * Reetz, M.T. ; Kesseler, K.; Schmidtberger, S.; Wenderoth, B.; Steinbach, R. Angw Chem Int Ed Engl, (19831, 22, 989 E ct, =c, Me
E t 11CN =CHCH n B u TMS
~
Et%{
BF3*0Et2, CH2Cl -78OC,
0
;
'CHO
H,
E
OH
t
y
y
30)
(70 86%
5 min Chem Lett, (1983), 1409
* Ando, W. ; Tsumaki, H.
--
1. nBuLi
2.
OH
I
CH3(CH2)3CHCH=CHMe
@=A r n b e r l y s t Cardillo, G.
3. I 2
-__)
@-NMe3+F-,
PhH
A26(F-) r e f 1ux
* : Orena, M.;
,f:MEM
1.
MeS
Braun, M.
19
co*
68%
Porzi, G.; Sandri, S.; Tomasini, C. J Org Chem, (19841, 2, 701 PhCHO
2 . HgC12
* : Hild, W.
CH3(CH2)3CHCEt
a q . MeCN
*
H OH
PhA/=2=2/ 57% (92% ee)
Angew Chem Int Ed w, (19841, 23: 723 ----
-
ALCOHOL
SECTION 330
KETONE
&"
0
I \
PhS02N-CH P h
*
KN(TFIS)2 -78°C
333
78%
*
Davis, F.A. ; Vishwakarma, L.C.: Billmers, J.M.; F i n n , J. J Org Chem, (19841, 49, 3241 -
*
-
1. nBuCH=CH2 PhH, 90°C
t
tB u C S N - 0-
Ax
*
t-BuO
2. Ni(R)
*
Curran, D.P. ; Scanga, S.A.; Fenk, C . J . -J Org Chem, (1984),
Osuka, A , * :
Taka-Oka, K.:
1.
0
I1
PhCCH3
Suzuki,
* H.
92%
3,3474
-.Chem
0;:"" ,
MeOH,
M o r i a r t y , R.M.:
HOU, K.-C.;
M o r i a r t y , R.M.;
HOU, K.-C.
Lett,
74%
(19841, 271
KOH
10°C
2 . 5% H 2 S 0 4 ,
H *-Bu (tto
CH2C12
*
19
P h C C H OH 54%
Prahash, I .
Org SE, (1985), 3, 138 Tetrahedron Lett, (19841,
-
25, 691
334 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 330
0
0
I1
!C6H1
PhCHO,
3CCH2Br
O°C
+,
OH
I1
!C6H1
I
3CCH2CHPh
nBu3SnAl
Et2 81 % 30 m i n * Tsuboniwa, N.: Matsubara, S.; Morizawa, Y.: Oshima, K. ; Nozaki,
H.
-
Tetrahedron Lett, (1984),
EtCHO,
CrC12
t BuCCHCH
-t
I B r
THF,
RT,
* Dubois, J.-E. ; Axiotis, G.;
t-Bu
"< H
iP r C H O
,OB.o
/
c =c
81 %
Bertounesque, E.
*03
Ph
Me
26, 4371
\
CH3
2 . N(CH2CH20H)3
Hoffmann, R.W.
Me
24h
Tetrahedron E,(19851,
1.
25, 2569
>
Me
9) 85 %
* ; Ditrich, K.
Tetrahedron E ,(1984),
1. 2 IDA,
THF
2. S n C 1 2
-
' I
3. EPrCHO,
25, 1781
O°C
4. H ~ O +
M
.
HO P 60%
(58% ee)
Narasaka, K.; Miwa, T.; Hayashi, H.; Ohta, M. Chem Lett, (1984), 1399
--
0
r
SECTION 330
ALCOHOL
1. nBuLi,
2.
0
P h 3 C II CEt
3.
THF,
PhCHO,
-
-75°C
(99
1)
0
OH
0
0°C
*
Ph,C W
HOH
335
KETONE
P Me
h
Ph,C+Ph
t
99%
OH Me
1 . A1Me3 2.
PhCHO,
3 . HOH
Ertas, M.:
Seebach, D .
40°C
*
(5
PhCCH2CH3
nC H C H O , C H 2 C 1 2 - 3 7 PhBC12, i P r N E t 2 -78°C
*
Hamana, H. ; Sasakura, K.;
0 HO Ph%.Pr
Me (99
1 . NaN(TMS)2,
II
PhCCH2CH3 2. &N SO&
Davis, F . A . * ; Haque, M.S.
0 HO P h h . P r Me 1) 52%
SugaSawa, T. Chem Lett, (1984), 1729
-_c
0
99%
Helv Chim Acta, (19851, @, 961
0
II
95)
THF,
+
-78°C
0
Ph
77%
( 6 8 .5% ee S )
0 -J Org Chem, (19861, 51, 4083
PhIO, BF3 E t 2 0 , HOH OMe
Moriarty, B.M.*,’ Prakash, 0 . ; Duncan, M.P. Synthesis, (19851, 943
6 5%
336 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
H,
OH
0 II
1 . PhI(OCCF3)2, CHC13,
8OoC
10h
*
2. S i 0 2
* Tamura, Y. ; Yakura, T.;
0; CS iMe3
SECTION 330
77%
Haruta, J.; Kita, Y. Tetrahedron E,(19851, 26, 3837
nPrCHO, CsF, RT DMI,
3 min
'Q
OH
*
nPrCHC
-
II
0
55%
DMI = 1 ,3-dimethyl imidazol idin-2-one
*
Ricci, A.; Degl'Innocenti, A . ; Chimichi, S.; Fiorenza, M.; Rossini, G.; B e s t m n , H.J. --J Org Chem, (19851, 50, 130
'
CHO (CH20),,
EtOH,
Et3N
-
I +
6OoC,
,
* I d 64%
*
Matsumoto, T.; Ohishi, M.; Inoue, S. J Org Chem, (19851, 50, 603 1 . M e 2 C u L i , THF, 2.
O O C ,
3.
H,Ot
-78OC
15 min
3
* Koreeda, M. ; Luengo, J.I.
quant.
---J Am Chen Soc,
(19851, 107, 5572
SECTION 330
ALCOHOL
0
I1
EtCHO,
CH 2 = C H C C H
-
4OoC,
40h
1 % HRh( PPh3)4
*
acetone
(C-Tyr-OEt)2,
NO2
40°C,
w
CH C C C H E t 311 78%
Chem Lett, (19851, 1875
%to, S.; Matsuda, I. ; Izumi, Y.
Zn(N03)2,
337
KETONE
"$
*
HOH
\
NO2
24h
*
Watanabe, K. ; Yamada, Y.: Goto, K. Bull Chem Soc Jpn, (19851, ----
58,
Hob
1 . LDA
2 . TMS-C1
3. TPPO, C H 2 C 1 2 , - 7 8 ° C
4.
83%
PPh3
1401
69%
TPPO = t r i p h e n y l p h o s p h i t e o z o n i d e
*
Iwata, C. ; Takemoto, Y.; Nakamura, A . ; Imanishi, T.
C H =C
2 \
/SiMe20i
Tetrahedron Lett, (i985),
Pr
1 . mcpba, O O C ,
?'gH1 3
*
Tamao, K. ; Maeda, K.
2.
3227 0
CH2C12
5h
26,
+
II nC6H1 3CCH20H
3 0 % H 2 0 2 , KHF2 K H C 0 3 , MeOH RT,
3h
Tetrahedron Lett, ( 1 986) , 3, 65
72%
338 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
&
"'0
M e 0 OMe
e , KI KO;,
O
*
MeOH
M e 0 OMe
H
18)
(82
77%
* Shono, T. : Matsumura, Y.;
Inoue, K.; Iwasaki, F.
JCS Perkin ---
I , (19861, 73
0
ti
II
HO
CH 2 = C C C H 3 nC5H1, CHO
DABCO,
SECTION 330
THF,
72h
nC5H1 CHCCCH3 I1
t
CH 2
*
Basavaiah, D. ; Gowriswari, V.V.L.
65%
-
Tetrahedron L e t t , (1986),
OH
K2Fe04, A1203, PhH
I
PhCHCH2CH20H
Kim,
3, 2031
C u S 0 4 . 5 H 2 0 , R T , 4h
* K.S. ; Song, Y.H.;
Q
*
P h C C H 2 C H 20H 95%
Lee, N.H.; Hahn, C.S.
-
Tetrahedron L e t t , (1 9861, 0 c1 II I 1 . PhS-CHFC6Hl3
3, 2875
2 . PhS-/tBuOK 3. 2.2 mcpba 4. HO-
*
Satoh, T.: Motohashi, S.; Yamakawa, K.
*
-
' c 6 H 1 8 0 H 83%
Tetrahedron L e t t , (1 9861,
3, 2889
SECTION 330
ALCOHOL
0
-
KETONE
339
OH
0
Sm/CH212
II
t
C H ~ C\ C /H - C H ~ C ~ H ~
I
II
C H ~ C C H ~ C H ~ C ~ H ~ ,
THF/MeOH , - 9 0 ° C
'0'
Molander, G.A.
* ; Hahn, G.
p
81 %
J Org Chem, (19861,
-78"C,
Maruoka, K . ; Hasegawa,
2596
& V
TiCl 4 , C H 2 C 1
~ ~ 'OSiMe, ''ph
51,
Ph
30 m i n
81 %
* M.: Yamamoto, H. ---J Am Chem Soc, (1986), 108,3827
1 . E t C H O , LBuMgBr
/
Tol'
T H F / E t 2 0 , -78°C
II 0
,,d1'\ 9
CH2CCH3 2 . A l / H g ,
THF,
*
Et 67%
0°C
a.
(64% ee)
Schneider, F.
* ; Simon,
0
R.
Synthesis, (19861, 582
4% P d ( P P h 3 ) 4 ,
PhCH3
/ \ PhCH-CHCH20H
t
P h C H 2 C C H 20H
s e a l e d t u b e , 140°C
62%
60h
Vankar, Y.D.
* ; Chaudhuri,
N.C.;
Singh, S.P.
S 2 Coamun, (1986),
16, 1621
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
340
--
-
SECTION 331: Alcohol, "hi01 Bn-0 MeiikcHO H
SECTION 332
Nitrile
1 . TiC14, C H 2 C 1 2 - 78 " C
Bn 0
BnO
Me
*
(80
H OH 20)
2 . TMS-CN, -78°C l h 98% * Reetz, M.T. ; Kesseler, K.: Jung, A. Angeu --C h a t Int Ed Engl, ( 1 985), 2, 989 1 . B r C H 2 C N , g l y m e , Ni 85"C, 4 0 m i n
PhCHO
2 . aq. HC1
*
Ni
*
OH
I
t
PhCHCH2CN
84%
= N i I / L i / n a p h t h a 1 e n e / g l yme/RT/12h
Inaba, S.: Rieke, R.D.
Review:
.-v1
k
Albright, J.D.
'
*
-
*
-
Tetrahedron Lett, (19851,
26,
155
Equivalents from Cyanohydrins, Cyanohydrins and a-Dialkylaminonitriles"
i
~
Tetrahedron, (19831,
3,3207
SECTION 332: Alcohol, Thiol
-
Olefin -- -
Allylic and benzylic hydroxylation (C=C-CH + C=C-C-OH, etc. is listed in Section 41 (Alcohols and Phenols from Hydrides).
QQ
SiMe,
dSiMe3 1. nBuLi, -85°C -I
Lo
8h 2 . O"C, H C 1
*
no y i e l d ( t h r e $ : e r y t h r o = 91 : 9 )
Mikami, K.; Kimura, Y.; Kishi, N.; Nakai, T.
--J Org Chem,
(1983),
48,
279
SECTION 332
ALCOHOL
CH3CH=CHCH2SiMe3
(L)
iPrCHO TiCl
-*CH2C1
- OLEFIN
341
+ , + + Me
-78"C, lh
( 97 92%
*
3)
*
Hayashi, T. ; Kabeta, K. : Hamachi, I : Kumada, M. Tetrahedron'Lett, - (19831, 2, 2865 0
LiA1H4 ~
~~
CH2CH20H H-C r N H M e
7
95%
( 1 00%
ee
CH N H P h * Sato, T. ; Gotoh, Y.; Wakabayaihi, Y.: Fujisawa, T. Tetrahedron Lett, (19831, 2, 41 23 0 0 It II HC(CH2)4CnBu
,
2 CH2=CIMe 4 CrC12
S )
C H 2 = C CI H ( C H 2 ) 4 C n B ~ OH
DMF, 25"C, 1 5 min
94%
Takai, K.*; Kimura, K. ; Kuroda, T. ; Hiyama, T.*; Nozaki, H. Tetrahedron Lett, (1983), 2, 5281
M e 2C = C = C H B r
P hCH *OL i , LB u OL i
*
OH
I
PhCHCH =C=CMe2
TH F / hexan e , r e f 1 ux 2h 65% * Harada, T.; Nozaki, Y.: Oku, A. Tetrahedron Lett, (19831, 2, 5665
342 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 Li
SECTION 332
1.
2 . PhCHO
Wuts, P.G.M.
* : Thompson,
( t h r e o : e r y t h r o = 1OO:l)
P.A.; Callen, G.R. (19831,
-J Or6 Chm,
-
JX , Mn,
48,
5398
THF
c a t . 12, reflux overnight R = LBu X = Br ( a x : e q = 57:43) Hiyama, T.*; Sawahata, M.: Obayashi, M. Chem Lett, (1983), 1237 -R
R = H X = I
*
C a ( H g ) , T H F , 0°C 4h
>
R
89%
59%
Imamoto, T. ; Kusumoto, T.; Tawarayama, Y.; Sugiura, Y.: Mita, T.: Hatanaka, Y.; Yokoyama, M. --J Org Chem, (1984), 2, 3904
R = H
X = Br
P b , Bu4NBr, D M F ,
RT
86%
*
Tanaka, H.: Yamashita, S.; Hamatani, T.; Ikemoto, Y.: Torii, S. Chea Lett, (19861, 1611
--
T H F , -3OOC 1 .5h 2 . C H 2 ' C H C H O , -30°C-RT 3. aq. NH4C1, HC1 1 . Yb,
Phi
OH
*
I
Ph CHCH =CH2
66%
YoI$oo, K.: Yamanaka, Y ; Fukagawa, T.; Taniguchi, H.: Fujiwara, Y. Chem Lett, (1983), 1301
--
*
SECTION 332
ALCOHOL
-
OLEFIN
343
48%
DeRenzi, A.;
Panunzi, A.*:
Saporito, A . ; Vitagliano, A. 993
JCS Perkin 11, (19831, ---
1. nBuLi, -3O"C, CH30CH20CH2CH'CH2 2 . Et3A1,
--."A
THF
No>
l h -78°C
HO
3 . nBuCHO,
* Y . ; Yatagai,
*/
Yamamoto,
- 7 8 "C-RT
90%
H.; Saito, Y . ; Maruyama, K .
-J org
1. iBu3Al
Chm, (19841,
9, 1096
-$
, CH2C12, 25°C
2 . HC1 , 1 5 m i n
Mori, I . ; Takai, K . ; Oshima, K.: Nozaki, H. Tetrahedron, (19841,
82%
110,
4013 H
3.
a q . HC1
*
OH
(98% ee R)
Kawasaki, M.; Suzuki, Y.; Terashima, S. Chem Lett, (19841, 239 --
344 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
HOCH H O C H C S C C H OH
*
t
-
Et20/THF, RT
reflux
SECTION 332
2 , C =[: H'-
-
60%
Ishino, Y. ; Wakamoto, K.; Hirashima, T. Chem Lett, --
CH-OH
(19841, 765
S n , A l , RT t
aq. dioxane
c a t . AcOH, 24h
61 %
Nokami, J.*; Wakabayashi, S.; Okawara, R. Chem Lett, --
(1984), 869 OH
R'X
RCHO
S n , MeOH, e
R = P h , X = Br
I
RCHR '
t
-
AcOH, P t e l e c t r o d e ? 55"C, c y c l o h e x a n e
R ' = CH2CH=CH2
*
Uneyama, K.; Matsuda, H.; Torii, S.
91 %
Tetrahedron Lett, ( 1 984) , 3,601 7
R = iPr R ' = CH2CH=CH2
X = Bt(Q)2
-
-7!"c 3 . NaOH,
86% (90% e e S)
H2T2
Jadhav, P.K.; Bhat, K.S.; Perumal, P.T.; Brown, H.C. R = 3C6Hl3 R = (r-CH2CH=CHPh) X = OAc
-J Org .-Chem,
(19861,
51, 432
Pd(. P P h 3 I 4 , Sm12 THF, O'C, 2.5h
Tabuchi, T.; Inanaga, J."; Yamaguchi, M.
-
*
t
Tetrahedron Lett, (19861,
63%
3, 1195
SECTION 332
ALCOHOL
R = CH2-Tol R ' = CH2CH=CH2
-
345
OLEFIN
QCHZN3
-18OC
A
*
Sn(OTf)*, CH2C12 X = AliBu (87% ee S ) Mukaiyama, $.; Minowa, N.; Oriyama, T.; Narasaka, K. Chem Lett, (19861, 97 R = Ph
--
R ' = CH2CH=CH2 X = OP(O)[OPhI2
SnF2-Et2A1C1
95%
>
Matsubara,,S.; Wakamatsu,. K.; Morizawa, Y.; Tsuboniwa, N.; Oshima, K. ; Nozaki, H. Sots, (19851, 58, 1196 -.Bull Chem R = Ph 1 . B i , DMF , R ' X R ' = CH2CH=CH2 94% 2. RCHO X = Br
-
-
*
Wada, M.; Akiba, K. R = Ph R'
= CH2CH=CH2
*
-
Tetrahedron Lett, (19851, BiCl,,
X = B r
*
Zn
26, 4211
.>
THF, RT
99%
Wada, M.; Ohki, H . ; Akiba, K. Tetrahedron Lett, (19861, R = PhCH2CH2 R ' = CH2CH=CH2 X = GePh3
%no,
-
BF3:OEt2, CH2C12 -78°C - RT
*
55%
H.; Miyazaki, Y.; Okawara, M.; Ueno, Y.
Synthesis, ( 19861, 776
(E)-PhCH=CHCH2C1 PhCHO
3,4771
SnC12-A1,
aq. THF
*
>
Ph Ph
(threo:erythro
Uneyama, K.; Nanbu, H.; Torii, S. Tetrahedron Let.t, (1986),
87%
= 98:2)
3, 2395
346 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 332
1. CH~=CH~H,
0'
PhCHO
2.
Tsai, D . J . S . :
P hCHCH 2CH =CHTMS
91 7: ( -Z :_E
120°C
= 78:22)
Organometdllics, (1983),
Matteson, D.S.
2,
236
1 . 2 EBuLi HO 2 Ph
A
2.
TiC14
3.
PhCH2CH2CH0
OH
*
4 . Me S i C H 2 C H = C H 2 5 . TM?I Imwinkelried, R.: Seebach, D.
*
I
PhCH2CH2CHCH2CH =CH2 (80% ee R )
Angew Chem Int Ed Eslgl, ----
3.
(1985),
75%
2, 765
NH4C1 /NH40H/HOH
Taber, D.F.*; Dunn, B.S.; Mack, J.F.; Saleh, S.A. J Org Chem, (1985), 50, 1987 OH
I
C H 3 C H CH C E C H
TiC14, CH2C1 2,
Me3A1
+
-78°C
87%
PH
CH3CHCH2CH =CHCH3
80%
2h
Wing, J . C . ; Fgrguson, G.S.; Moore, D.W.; Thompson, D .W.
J O m Chem,
Schultz, F.W.;
(19851,
50,
2124
SECTION 332 SiMe,
-
ALCOHOL
0
/ \
OLEFIN
, TiC14
1 . CH2-CH2
CH2C1 2 , - 1 00'C-RT 2 . 0.1N K O H
C a m , S.A.: Weber, W.P.
*
347
*
@OH
86%
J Org Chem, ---
Me3SiOOSiMe3, VO(acac)2,
(1985),
50,
2782
25°C
CH2C12
5h
Matsubara, S.; Okazoe, T.; Oshima, K.;
85 %
* Takai, K. : Nozaki, H.
Bull Chem Soc *,(19851, 58, ---
A
1 . iPrCH,CHO
Bubnov, Y.N. * ; Etinger, M.Yu. Tetrahedron Lett, (1985),
JC'
1 . NaBH4, C e C 1 3 , MeCN -15"C, 5 m i n 2. aq. HC1
Me0
844
->
bO"
26,
94%
2797
Me0
*
8 5%
Lakshmy, K.V.: Mehta, P.G.; Sheth, J . P . : Trivedi, G.K. Org Prep -hw: Int, (1985), 3, 251
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
348
SECTION 332
1 . A1Me3, T i C 1 4 E t \ Me20, p e n t a n e EtCH=CHCH2CH20H
20°C, 2 . HOH
(L) Moret, E.; Schlosser, M.
0
HO
+.Ph
CH2CH20H
Me / c = c \ H
5 5% Tetrahedron E ,(1985) , 26, 4423
*
1 . PhI,
*
3h
I
"gP Ph
2% Pd(PPh3)2(0Ac)2
Pip,
10h,
6OoC, 4 % C u I
2 . HCOOH
*
7 0%
Arcadi , A. ; Cacchi , S.*;
Marinelli , F.
Tetrahedron, (19851,
* p
MeCeCl THF/Et20, Me0
9, 5121 h
'
+
-78°C
OMe
98%
30 min
Imamoto, T.*: Sugiura, Y. 2 Organanet Chem, (19851, t(, 7
aB.o 1
EtCHo
1. EMeCH=CHFH c1 Pet ether 2 . N(CH2CH20H)3
Et+
OH -
VC' +
E
Me
285,
+
q
Me
65%
5%
C021
CI
(96% ee)
Hoffmann, R.W.*;
Dresely, S.
Angew Chem Int Ed Engl, (1986),
c
3,189
SECTION 332
-
ALCOHOL
349
OLEFIN
L i I
4 [ CyN=Bu/MeMgBr]
w O"C,
20h 85%
*
Masset, P.; M a M a , S.; Viala, J.; Falck, J.R. Tetrahedron Lett, ( 1 9861,
-
1 . 4 CH2=CHCH2Br,
-5OC
OH
(+)diethyl tartrate 5 PhCHO 2.
THF, NaH, NaH
I
w
Sh
3, 299
P hCHCH2CH =CH2
82%
3 . SnC12
( 6 2 % ee S )
Boldrini, G.P.; Tagliavini, E.; Trombini, C.; Umani-Ronchi, A. JCS Chem Comn, (1986), 685
---
OTf
I
fiCl O H 2 1 C=CH2
PhCHO, cat.
CrC12,
NiC12,
DMF
25°C
w
H CCHPh c C 1 o 21 1 OH
87%
*
Takai, K. ; Tagashira, M.; Kuroda, T.: Oshima, K.; Utimoto, K.: Nozaki , H. J Am Chem Soc, (1986), 108,6048 ---CH 3
PPh3, THF,
iPrOH
I
n P r C H = C H C C H 20H -
I
N 02
*
5% P d ( P P h 3 ) 4 , NaBH4,
5h
0°C
n P r CH=CH YHCH 2 OH
97)
Me
86%
+
n P r C H2CH= C'
CH
'CH
(3)
Ono, N. ; Hamamoto, I.; Kamimura, A.; Kaji, A. --J Org Chem, (19861, 51, 3734
20H 3
SECTION 334
350 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
+
Ph3PCH2CH2CH20H C 1 PhCHO
K2C03, iPrOH, 1 2 h
t
P h C H =CHCH2CH20H
84%
Cheik-Rouhou, F . ; Le Bigot, Y.; El Gharbi, R.; Delmas, M.*; Gaset, A. Commnz, (19861, 16,1617
Review: '!Double Asymmetric Synthesis and a New Strategy f o r Stereochemical Control In Organic Synthesis" Masarnune, S.
* : Choy, W.:
Petersen, J.S.; Suta, L.R.
Angew Chem Int Ed Eh@, (19851, 24, 1
Also via: Acetylenes-Alcohols (Section 302) SECTION 333: Aldehyde
, -
-
Aldehyde
'
1 . P h P h , 0 2 , MeCN D C A , 1 0 ° C , 3 0 min 2 . Me2S
DCA
t
88%
9,lO-dicyanoanthracene
*
Schaap, A.P. ; Siddiqui, S . ; Prasad, C.; M.
Palomino, E.: Sandison,
Tetrahedron, ( 1 9851,
SECTION 334: Aldehyde
-
Amide
No Additional Examples
41,
2229
SECTION 336
SECTION
E
335: E d (
q
-
-
ESTER
Amine
-9 Bn
Bn
I
I
(-Z ) - E t C H z C H O T M S , T H F BF3.0Et2, -78OC,
* Lounasmaa, M.
Koskinen, A . ;
c
351
94%
JCS Chem Carm, (19831, 821
1 .(MeS)2CH2, L B u O C l tBuOH, 2OoC, 4h
*
24h
2 . NEt3, CH2C12
b
Claus, P.K. ; Jgger, E.: Setzer, A . Honatsh Chem, (19851,
OCHO 1 . Br2
2. N E t 3 , H O H
Y
Bn
72%
116,1017
* Bn quant.
Duhamel, P.*: Kotera, M.; Monteil, T. Bull Chem Soc Jpn, (1986), ----
-
SECTION 336: Aldehyde
-
Ester
1 . Ac20/Py Ph
s To,
*
3,2353
2. C u C l , A c O H
*
OAc Ph
55%
Ogura, K. ; Fujita, M.: Inaba, T.; Takahashi, K.; Iida, H. Tetrahedron Lett, (19831, 24, 503
352 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . Fe(CO)$
-2
, THF
DcozEt co
0
*
2* 3 . AcOH
C02Et
SECTION 336
II
HCCH2CH2CH(C02Et)2 62%
Tamblyn, W.H.
* ; Waltermire, R.E.
-
Tetrahedron Lett, ( 1 9831,
* -J Org Chem, Coates, R.M.
Cummins, C.H.:
(19831,
1. n B u L i , T H F , -78°C
iNHLBU-
H CnB u
2 . E-MeCH=CHC02Me
3 . AcOH
24,
2803
118, 2070 CHO
*
I
CH3CHCH2C02Me 60%
*
Baldwin, J.E. ; Adlington, R.M.; Bottaro, J.C.; Jain, A.U.: Kolhe, J.N.; Perry, M.W.D.; Newington, I.M. JCS Chem Coma, ---
1 . l o 2 , FleCN, h v methylene blue, OMe
*
2 . 36°C
93%
(19841, 1095
- 2 O O C
C0,Me no y i e l d
Jefford, C.W. ; Boukouvalas, J.; Kohmoto, S. Tetrahedron, ( 1 9851, 2, 2081
SECTION 337
ALDEHYDE
1 . LDA,
Ph
- ETHER
353
THF
2 . Me3SiC1
I I
CH3CH2CHC02Me
CHO
3 .tBuN=CHCN,
MeCN
I
*
C H CH CC02Ple
21
c a t . TMSOTf ~ . * C U ( O A C ) ~9,5 % MeOH
Ph
: Sekiya, M.
Okano, K.; Morimoto, T.
85%
JCS Chem Comn, (19851, 119
---
1 . CH3C(OEt)3 CHO
CH3CH2COOH , 2 0 0 ° C MeCH=CHCH20H
+
2 . a q . HC1
3 . 03, - 7 8 ° C 4 . Me2S, 0°C
68%
*
Carman, L.; Kwart, L.D.; Hudlicky, T. *Comnun, (19861, 1.
Enders , D Knoch, F. -.SECTION
*
Me
2 . LDA, THF, TMEDA, 3 . E-MeCH=CHC02Me 4.
16,169
G O M e NH2
EtCHO
I
CH3CHCH2C02Et
0 , C H C1
0:C
OHCd'CO,Me Me
-78°C
. ; Papadopdulos,2K. ;2Aendenbach, B ,E .M. ; Appel , R Tetrahedron E,(1 986),
337: Aldehyde
-
58%
;
3, 3491
Ether, Epoxide, Thioether
1 .E-cBuOCH=CHCO2Me H CmC 0 2Me
iBuOH
2. Dibal-H 3 . MnO
Vo Quang, Y.; Marais,%.;
*
nB uOCH =CH C H O
Vo Quang, L.: Le Goffic, F.
Tetrahedron E,(1 9 8 3 ,
61 %
2, 5209
354 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
(CO)5MnSiMe3, PhCH 2CH 2 C H 0
Brinkman, K.C.:
LBuOH
OTMS
(C0)5MnH, CD3CN, 50°C >
Gladysz, J.A.
SECTION 338: Aldehyde
SECTION 338
I I
PhCH2CHCH0
7d
*
78%
Organcme$allics, (19841,
- Halide, SulfOMte
3,
147
CI
TMS-C1 , CH2C1 MeCH=CHCHO
(L)
HOCH2CH20H -1 5 ° C - r e f l u x
-
Tetrahedron Lett, (1984),
G i l , G.*
cH ( cH
L
1 . BBr3, 2 . KOAc ) CIC H
Satoh, Y . ;
25, 3805
pH 5
*
3. 30% H202
Br 1 CH ( C H ) 4 C H C H 0
Tayano, T.; Koshino, H . ; Hara, S . : Suzuki, A . Synthesis, ( 1 9851, 406 t
1 0 % ~ = C H O Hc i
nBuCHO
88%
CC14,
c1 2
70°C
65%
-
c1
I
n P r CH C H 0 99%
SECTION 339
ALDEHYDE
-
355
KETONE
I
r
TMS-C1,
o*o U
41
KI,
MeCN
*
0
Ll
2 2 0 ~ ,90 m i n
sieve,
F2,
FCC13
65%
F I
>
PhCH=CHOS iMe3
P hCH C H 0
-78’C
72%
i
4
*
Purrington, S.T. ; Lazaridis, N.V.: Bumgardner, C.L. Tetrahedron Lett, (19861, 27, 2715
-
SECTION 339: Aldehyde
6’
- Ketone
Br 1 . PhSCHTMS,
ZnBr2
2 . mcpba
3. heat
4 . H30t
Ager,
* D.J.
45%
Tetrahedron Lett, (1983), 2, 419
“‘cf ’
0
HO
I\
OH
PdC12
CH2=CHCCH3 CuCl,
*
DME,
>
O2
5OoC, 2 0 h
5 u“‘ 0
0
Me
*
8 6%
Hosokawa, T. ; Ohta, T.: Murahashi, S.I. JCS Chea .-Comn, (19831, 848 -
-
Me
356 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Akgiin, E.; Pindur, U.
*
Synthesis, (19841, 227
1. tBuN=C, n PrCH -
,cu Bu
-
-78°C
=CHCHO
SECTION 341
, BF3*0Et2
0
II
0°C
-
2 . H30+
-
*
nBuCCHCH2CH0 I n Pr 90%
Ito, Y.; Imai, H.: Matsuura, T.; SaeguSa, T. Tetrahedron Lett, (1984), 25, 3091 1 . P0Cl3,
n
D M F , 45OC lh
2 . HOCH2CH20Na, 2h
*
Huet, F.
RT
-
*
45OC
DHO 3 6%
Synthesis, (1985), 496
SECTION 340: Aldehyde
-
Nitrile
No Additional Examples SETION 341 : Aldehyde
-
Olefin
For the oxidation of allylic alcohols to olefinic aldehydes see also Section 48 (Aldehydes from Alcohols).
ALDEHYDE - O L E F I N
SECTION 341
C H 2TMS
357
CH 0
PhIO
I
I
B F 3 * O Et 2
Ochiai, M.;
* E.
Fujita,
dioxane
T e t r a h e d r o n s , (19831,
TMSOOTMS
OH
I
CH,CH(CH,)~CH=CHCH,OH
RuCl 2 ( P P h 3 ) 3
63%
2, 777
OH 1 CH~CH(CH~)~CH=CHCHO
70% Kanernoto, S.; Oshima, K.*;
Matsubara, S.; Takai, K .
E ,(1983), 2, 2185
Tetrahedron
CH2=CHCH0, - 2 4 ° C
K - 1 0 c l a y / F e +3 CH2C1 Laszlo, P.*;
Lucchetti, J .
Tetrahedron
1. tBuOK, 2 . DMAP,
CH2=CHCH2NHMe
THF, THF,
-78°C
-
Me2S04,
-78OC -78°C
RT PhH,
5 . a q . HC1, Senaratne, K.P.A.
RT
Tetrahedron
9..
E ,(1984), 25, 2147
3 . c y c l o p e n t a n o n e , THF 4.
Gilbert, J.C.*;
60%
reflux
I
49%
E,( 1 9841, 25, 2303
358 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
MeSCH = C H C H 2 S 0 2 T o l
zcCgH17 ) 3 NMeCl K O H , D M F , - 1 5OC 2 ' 1 2 H 2 5 Br 2 . TiC14, CuC12
+ !Cl
SECTION 341
2H25CH=CHCH0
RT - 5OoC 3 . K CO D M E , RT Ogura, K . ; Iihama, T.; Taiahaiii, K . ; Iida, H. Tetrahednxl Lett, (1984),
59%
*
-
1 . Me2NCH2CN, DMF K2C03, 48h 2 . A g N 0 3 , THF
Br
25, 2671
w
E t 2 0 , HOH Stela, L.
*
Tetrahedron E,(19841,
PhCH=CHCH20H
92%
25, 3457
K 2 F e 0 4 , a q . NaOH
*
PhCH=CHCHO
B n N E t 3 C 1 , P h H , 25OC 1 .5h Kim, K.S.*; Chang, Y.K.; Bae, S.K.: Hahn, C.S. Synthesis, ( 1984) , 866 Et2A1SPh, DCE 25' C ,
15 min
*
95%
YHO
,?""
V'8 4 %
(E : I = 39:61)
Takai, K . ; Mori, I . ; Oshima, K.*; Nozaki, H. WiIl Chen~Soc (1984),
---el
57, 446
SECTION 341
ALDEHYDE
Ph3As-CH2CH0 B r K 2 C 0 3 ( t r a c e HOH)
O U 0 CHO
Et20/THF,
* Y. ; S h i ,
HO 0 ,.H ' 1 OH21 S n w Bu
E tOCH=C
\
Me
*
3h
x
0
0
W P C H O 91 %
L.; Yang, J .
-
Tetrahedron Lett, (19851,
( PhIO)n,
26,
6447
DCC
"C, O H 2 1 C H = C H ( C H 2 ) 3 C H 0
B F 3 * O E t 2 , RT
77%
12h
Ochiai, M.; Ukita, T.:
/C H 0
RT,
359
OLEFIN
-
+
x Huang,
-
1.
Nagao, Y . ; F u j i t a , E. JCS Chem Corn, (19851, 637
---
EtMgBr,
-
0°C
Et20
RT
2 . a q . NH4C1,
0°C
/
*
EtCH=C
\
CH 3 Me
88% * Spangler, C.W. ; Tan, R.P.K.; Gibson, R.S.; McCoy, R.K. Syn CamRln, (19851, 5, 371
03
Me0
Me0
1 . CH(OEt)3, BF3.0Et2,
2 . NaBH4,
CH2C12 iPr2NEt
MeOH
3 . 6N H C 1
DasGupta, R.; Ghatak, U.R.
WCH
Me0 \
76%
*
Tetrahedron=,
(19851,
26, 1581
360 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 341
Me I
OTBS
O
H
C
Me
TESCH=NtBu L
V secBuLi
* Schlessinger, R.H. ; Poss, M.A.; awe
OHC,
0-TB S
r;nrdv 77%
Richardson, S . : Lin, P.
Tetrahedron E ,(19851,
CH2=CHCH0, cat.
RT
Yb(fod)3
48h * Danishefsky, S. ; Bednarski, M.
26, 2391
YHO
MeC
*
60%
Tetrahedron Lett, (1985) , 26, 2507
1 . 5% P d ( P P h 3 ) 3 ,
Ph N
Y
2.5% CF3COOH,
PhH 50°C
2 . 0.5N H C 1 , RT
* Murahashi , S. ; Makabe, Y.
*
I
Me 78%
Tetrahedron
s, (1985), 26, 5563
* 50°C, 4 h
Ph I CH2=CHCH2CCH0
88%
\I
/\
(E : Z- = 7 : 3 )
*
Suzuki, S.; Onishi, T.; Fujita, Y.: Misawa, H.; Otera, J. Bull Chem Soc *,(1986), 3,3287 --Also via: B-hydroxyaldehydes (Section 3210
AMIDE
SECTION 343
SECTION 342: Amide
n-NT 9 0
B
0 Et
-
-
361
AMINE
Amide -
1 . L D A , T H F , -78°C 2 . CH2=CHCH2CH2Br
*
T H F , -78 - 0°C 3 . O " C , 3N H C 1 4 . a q . Na2C03
87%
Fukuyama, T .*; Frank, R .K. ; Laird, A .A.
-
Tetrahedron Lett,
;
CH3CN=C
nBu
PhLi
/
\
*
TH F
CNHOFSe *
Lipshutz, B.H. ; Huff, B.; Vaccaro, W.
3501
II
CH3CNHCH2CCNHMe
A
Ph
87%
Tetrahedron Lett, (19861, 9, 4241
-
Also
0
It
nBu -
II O
0
via: Dicarboxylic acids (Section 312); Diamines (Section
SECTION .---
343: h i d e
-Amine
1 . secBuLi, TMEDA -78"C, THF
2 . TsN3 3 . NaBH4, Bu4NHS04
Reed, J.N.:
* Snieckus, V.
82%
Tetrahedron E,(19831, 2, 3795
362 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
t$kBr
PhNHMe,
0
KrauS, G.A.
* ; Yue,
12h
PhCHO,
DMF,
4 N2 0 Ph
*
j : u
---
1 % Z ~ ( O A C ) ~ 3,h
SECTION 344: Amide
-
>
Fle2C=C
76%
(1984), 2, 4889
Me
,OTMS
I
'OB n
B n N H CH 2 C C 0 2 M e ~7
CF3S03H,
; Achi.wa,
II
EtCNHCH2CH2NHi P r
Ester -
Bn
Bn
0
18 0 ° C
* 2 Org Chem, M.J. -
Ikeda, K.
50%
Sridharan, V.: Thianpatanagul, S. JCS Chem Cam, (19841, 182
iP r N H 2 ,
0 'N
Bn ' N U
90°C
O
Grigg, R. ; Aly, M.F.;
tN7
6 5%
Ph
H $ J COOH
Fazio,
7OoC
J Org Chem, (1983), 48, 2936 ---
S.
0
SECTION 344
K.:
CH2C12
1 . 5 h , RT Sekiya, M .
I
Me
83 %
-
Tetrahedron Lett
SECTION 344
-
AMIDE
363
ESTER
1 . e - , Et4NC104 0
P t electrodes MeOH
0
Okita, M.; Wakamatsu, T.; Ban, Y.
*
*
21
C02Me
4 nBii2CuLi
T H F , -10°C
cope
O %
55%
Heten>cycles, (19831,
NHBOC I BrCH C H C H
cO,Me
20,
401 NHBOC
*
I
* (95% ee)
nBuCH CH CH -
74%
21
C02Me
Bajgrowicz, J.Al; El Hallaouri, A . ; Jacquier, R.*; Pigiere, Ch.; Viallefont, Ph. Tetrahedron Lett, (19841, 25, 2231
0
tBuOH,
C C H C C 0 E.1 e II II 0 0
aoZ
hv
I
*
48h
'0 7 0%
Gramain, J.-C.*; Remuson, R.; Vallge, D. J Org Chem, (19851,
50,
710
0
II
3 BnOCNH2,
0
MeOH
II
CH2=CHCHNHCOBn
PhSeCH2CH=CHC02Me 6 i P r 2 N E t
I
3 NCS, 0°C
C02Me
*
Fitzner, J.N.: Pratt, D.V.: Hopkins, P.B. Tetrahedron Lett, (1985).
63%
26,
1959
364 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
OH
I
NHS02T01
SECTION 344
PdC12, C u C 1 2
I
CH2=CHCHCH 2CH
A c O N a , AcOH
I
Ph
CO,
*
R T , 2d
I
S02Tol 80%
Tamaru, Y.; Kobayashi, T.; Kawamura, S.; Ochiai, H.; Yoshida, Z. Tetrahedron Lett, (1 9851, 26, 4479 C02Me
C H =CHMgB r
1
C1 - C - N H C B Z
I
THF,
H
-78°C
*
* Castelhano, A.L. ; Horne, S.; Billedeau, R.:
C02Me
I
CH 2=CH -C-NH CB Z
I
H
65%
*
Krantz, A . Tetrahedron Lett, (1986),3, 2435
1 . L i N ( T M S ) 2 , THF -78°C 2.
(BnOC0)2, -78°C II 0
t
3 . AcOH, 0 ° C
Gore, M.D.; Vederas, J.C.
*
(R:S =
BnOCO II 0 2:98)
-
87%
J org Chm, (1986),51, 3700
Related Methods: Acid-hide (Section 31 5); Acid-Amine (Section 31 6 ) ; Amine-Ester (Section 351 )
AMIDE
SECTION 345
SECTION 345: Amide
( C O ) 5Cr=C,
/
-
ETHER
365
Ether, Epoxide, Thioether P h C H = N Me
OMe
H
t Me
Hegedus, L.S. Anderson, 0. P
hv,
* : McCuire,
.
0
Et20
M.A.: Schultze, L.M.;
J Am Chem ----
I
-
Soc, (19841, 106, 2680
PhSeBr,
CH2=CHCH2CH-C-OMe
II NnB u
MeCN,
* A. ; Terao,
0
O°C
12h
PhSe
Uemura, S. JCS Chem Comn, (1986), 530
K.;
80%
--PhSeBr,
20°C
AcNH(CH~)~CH=CH* MeCN,
*
12h
Toshimit s u , A. * ; Terao, K . ; Uemura, S. (1986), 1 . PhOCH2CC1 NEt3 2.
Me
7 5% Yijun, C.:
Ph
Ph
Toshimitsu,
-
CAN
'"as
66%
51, 1724 I=!
phoLJ1?H 0
70% * Antonini, I.: Cardellini, M . ; Claudi, F. : Moracci, F.M. Synthesis, ( 1 986 1 , 379
366 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
(TMS)2NCH0,
PhCHO
OTMS
CC14
5% CF3S03TMS,
SECTION 346
I
t
RT
PhCHNHCHO
lh
63%
* Johnson, A.P. ; Luke, R.W.A.; Steele, R.W. JCS Chera Corns, (19861, ---
1658
Halide, pulfonate -- --
SECTION 346: AmIde
8 CI
c12
0 II
~
~
~
~
(
~
FeCl ~________) 2 ~ ~ = ~ ~ d ig 1 yrne
20 )
2
I
reflux, lh
*
60%
Tseng, C.K. ; Teach, E.G.; Simons, R.W.
Syn C o m u n , (19841,
0 II
AcOH,
CH3 ( C H ) 6CNH
RT,
Na02Br
fi, 1027 CH3(CH2)6CNHBr
3h
81 %
*
Kajigaeshi, S. ; Nakagawa, T.; Fujisaki, S. Chem Lett, --
(1984), 2045 0
0 II
K
JHTs * -Xle
\
Ts,
2 1 2 , K2CO3
* Hirama, M. ; Iwashita, M.;
78%
I
Et20, RT, 1 . 5 h
(2:E =
Yamazuki, Y.;
2.7:l)
* Ito, S.
-
Tetrahedron Lett, (1984),
25, 4963
SECTION 346
AMIDE
L
HALIDE
L
3 . a q . Na2S03
68%
*
Knapp, S. ; Rodriques, K.E.
Tetrahedron Lett, (1985), 7
NBS, DME-HC1
"'CNH-S
367
NEt,
1 . Me,SiOTf,
n
L
-
0 To 1
-5OoC,
*
l h
*
Zefirov,
25, 1063
Kolbasenko, S . I . ; Kutateladze, A.G.:
-J Org Chem USSR,
CN-Cl,s o 2 * N.S. ; Zyk,
S02Tol 88%
95:5)
Tamaru, Y.; Kawamura, S . ; Tanaka, K . ; Yoshida, Z. Tetrahedron Lett, - (19841,
CH2C12,
26, 1803
I
(I,E =
Zyk, N . V . ; N i k u l i n , A.V.; Z e f i r o v , N.S.
I
(19841,
*
-6O'C-RT
20,
1209
0"' 0
'''~~0S02
90%
N.V.;
Kolbasenko, S.I.;Kutaleladze,
-J org Chm,
(19851,
53, 4539
A.G.
368 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 347
1 . C0Cl2 2. C12
3 . HOH 4 . A1C13, C H 2 C I 2 ,
heat
5. HOH * Lambert, C.: Cai-llaux, B.; Viehe, H.G. Tetrahedron, (19851,
5 % a q . NaOH, CHC13
*a 70%
41,
3331
CI
SJ
c a t . Bu4NC1, 3 6 h Me Me ( 7 4 % c o n v e r s i o n ) 40% * Marcos, M . ; Castro, J.L.: Castedo, L.; Riguera, R . Tetrahedmn, ( 1 986), 9, 649 SECTION
3117:
Amide
-
Ketone
E t C H =C:
OTMS
nPr
-..& NHCO E t
0
1 . E t O CI1 N 3 ,
110°C
m
sealed tube
0
2 . Si02
56%
Lociuro, S.; Pellacani, L.*; Tardella, P.A. Tetrahedron Lett, ( 1 983),
-
OH
1 . NaH, T H F , 3 0 m i n 2 . C H 3L =i CO=hCCHFC3N
I
qj Blechert,
2, 593
c(+N"Ac
0
3 . HCOOH, H O H
* S.
Helv C h i m Acta, ---
65%
(19831, 68, 1835
SECTION 347
AMIDE
-
369
KETONE
ph%cHo
6 Mn(OAc)3 AcOH,
Nishino,
* H. ; Kurosawa,
1OO"C,
12 min 65%
Bull Chem Soc Jpn, (19831,
K.
01 , CH~CH=C< ,NMePh CH =C
2
THF,
\
CN
Ahlbrecht,
Me1
0
'3
CH 3
J
* H. ; Dietz,
7 6%
Synthesis, (19851, 417
M.
1682
0
t
2 . H,OS
56,
0
I1 1 . E t O C C l , MeCN, ,OTMS 2 . CH2=C, nPr MeCN,
Akiba,
* K. ; Nakatani,
RT,
0°C
~
W
N
V
o
40 bEt
2h
84%
M.; Wada, M . ; Yamamoto, Y . --J Org Chem, (19851, 50, 63
1 . CH3CN,
Hg(N03)2 0°C
2 . NaBH4,
Stevens, R.V.
* ; Albizati,
HOH
O
W Me NHAc
81% K.F.
--J Org Chem,
(1985), .-50, 632
370 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 348
0
1 . Ph3CNa, T H F
2. E N h P h , R T , 2 d
$Ph
3. H O H
*
Stamm, H. : Weiss, R. SECTION 348: Amide
-
0
65%
Synthesis, (19861, 392 Nitrile
CH2=CHCN, CH2C1 NaBH(OMe)3,
,,,, NHAc
-7OC
*
&CN
(I:E =
4:6)
Kozikowski, A.P.*; Scripko, J. Tetrahedron Lett, ( 1 9831,
1 . Hg(N03)2, CH2C12 AcNH2, reflux
nC H CH=CH2 - 4 9
2 . CH2=CHCN,
NaBH4, HOH
O°C
*
O&NH2 N H
1 . TMS-C1 , NEt3 ZnCl
2 . ZnC12, 80°C
3 . H30t * Rigo, B. ; Lespagnol, C.; Pauly, M. -J Heterocyclic
24, 2051
y 4H9
ACNHCH[CH~)~CN
Barluenga, J. ; Ferrera, L. ; Nijera, C. ; Yus, M. Synthesis, ( 1 984), 831 Y
7 0%
0
77%
H
91 %
e, (1 9861, 23, 183
AMIDE
SECTION 349
SECTION 349: Amide
-
371
OLEFIN
-Olefin
@
n
4 CF3COOH,
0d , & O H
0°C
t UATMS CH2C12, 2 h
0
*
90%
Hiemstra, H. : Speckamp, W.N.
4
Tetrahedron L e t t , ( 1 9831,
*
FVP
,C02Me N-O C 0 M e
( 500°C )
Chu, M.; Wu, P.-L.; Civre, S.; Fowler, F.W.
Tetrahedron Lett,
I
C02Me
*
40%
Tetrahedtqn Lett, (1 9861,
Koch, K.; Lin, J.-M.; Fowler, F.W.'
Y
( 6FV 5 OPO C )
Cheng, Y.-S.;
-
f
OAC
*
Lupo Jr., A.T.; Fowler, F.W. J Am Chem Soc, (19831, ---OB n
""3
0;; ,
0
3, 461
(19831, 24, 1581
'(TPhAcO
24, 1407
b 0
74%
105, 7696
178°C
62h
Bremmer, M.L.; Weinreb, S.M.
*
Tetrahedron
93%
E ,(19831, 24, 261
372 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
,,,,\Se P h
0
0
"
SECTION 349
0
I1
N HCO, Bn
BnOCNH2, MeOH iPr2NEt,
-
~
0°C
HO""'
NCS
RT
80%
Shea, R.G.: Fitzner, J.N.; Fankhauser, J.E.: Hopkins, P.B. J Org Chem, (1984), 2, 3647 0
II
E t 2 A 1 C1,
RCCH=CH2
-
Q
- 1 3°C
R =
9R$3 %
(99.5% endo)
*
so;
(93% ee)
Oppolzer, W. ; Chapuis, C.: Bernardinelli, G. Chim Acta, (19841, -.Helv R
*
&3/
E t A l C1
*
-2OOC
67,1397
Rb 73%
R =
Oppolzer, W.
* : Dupuis, D.
Tetrahedron Lett, (19851,
6HMe 1 . secBuLi,
-78°C
2 . "C6Hl3I
*
-
TMEDA
26, 5437
OyNHMe
>
OeCgH
Beak, P. ; Kempf, D.J.: Wilson, K.D. J Am Chem Soc, (19851, ----
58%
m, 4745
SECTION 349
AMIDE
-
1 . TiC14, CH2C12 0 - 25OC
OLEFIN
>
2 . CH2=C=CMeSiMe2tBu
OEt
\
0 - 2 5 " C , 45 m i n 3. NEt3 4. H O H * Danheiser, R.L. ; Kwasigroch, C.A.; Tsai, Y.-M. J Am Chem Soc, (1985), ----
HNEt2, PhH 20 atm C O
0 II
nPrCH=CHCH20P(OEt)2
* Murahashi , S. ; Imada,
_______)
C3CCH2SiMe3
I
(CH212
II
nPrCH=CHCH2CNEt2
Chem Lett, ( 1 985), 1477
81 %
a. HCOOH
>
I
Ac
107, 7233
(El
Bu4NC1 , 50°C
Y.
67%
0
Rh6(C0), 6
(L)
N-YHnPr I OEt
373
wPr
2v-7 AC
68%
*
*
Hiemstra, H. ; Fortgens, H.P.: Stegenga, S.: Speckamp, W.N. Tetrahedron Lett, (1985), 26, 3151, 3155
Crimaldi,
* J. ; Cormons,
-
A.
Tetrahedron E,(1986),
60%
3, 5089
374 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CH =C
2
iPr2NEt,
/CH2SePh
\
NCS
Ye
CH3
*
SECTION 350
s
CH 2 = C C H 2 N H C OtBu
I
Me
CH2=COhNH2 0
92%
Shea, R.G.: Fitzner, J.N.; Fankhauser, J.E.; Spaltenstep, A.: Carpino, P.A.; Peevey, R.M.; Tenge, B . J . ; Hopkins, P.B. J Org Chem, (19861, 52, 5243
Q tm-;;9
m-Pr
CH 2 C H = C H
I
3% P d 2 ( db a ) 3CHC1
> m-6~'
nPrCHNCC1
I8
nBu
m-BU
0 (83
18% PPh3
4
0
17)
69%
Henin, F.*; Muzart, J.: Pete, J . - P . Tetrahedron E,( 1 9861,
3, 6339
Review: IIAlkaloid Total Synthesis by Intramolecular Imino Diels Alder Cycloaddiltions"
Weinreb, S.M.
*
Accts Chem Res, ---
(1985),
18,16
Also via: Olefinic acids (Section 322)
- Amine ---
SECTION 350: Amine
1 . NH2CN, 2. HC1, nBuCH =CH2 -
NBS
EtOH
+
3 . Na2C03
4. a q . HC1,
J w g , S.-H.; Kohn, H q 7
2d
120°C
J Am Chem ---J Am Chem
Soc, Soc.
yH2 I
nBuCHCH2NH2
SECTION 350
AMINE
Q
1 . ( C ~ C O N O ) ~N ,O O"C, 4 0 m i n
"[
OMe
* R.C.
Et2?, b . MeLi,
2 . HOH
-
375
-78°C
58%
Organometallics, (1983), 2, 787
a. 3 LiNEt2,
-60
AMINE
t
2 . L i A 1 H 4 , THF
Becker, P.N.: Bergman,
CHO
-
NH,
VC14
-20
-
ooc]
2OoC, 1 7 h
&Me
*
Imwinkelried, R.; Seebach, D. Helv C h i m Acta, ( 1 984), --1 . T s - N = S = N - T s , P h H , RT 2 . P h M g B r , T H F , -60°C
3. P(OMel3,
MeOH
w
*
NHTS
-no *
THF, r e f l u x , 8 h Iahikura, M.; Kamada, M.;
3, 1496 NHTs
Natsugari, H.: Whittle, R.R.: Weinreb, S.M. ---J Am Chem Soc, (19841,
P d (QP P hC3 ) ql, ,K OB Hu 4 N B r
54%
* Terashima, M.
Synthesis, ( 1 984), 937
83%
106,7867
N
82%
376 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
9 KBar, H
RT,
2d
0 LN3
t
CH2C1 2/MeOH
SECTION 351
5 0%
* Matsumoto, K. ; Hashimoto, S.:
Ikemi, Y.: Otani, S. Heterocycles, (1984), 22, 1417
t
Y
PPh,Br-
1 . EDA, CHC13, 20°C 2 . 2 LBuOK, Et20 *
\1 PPh3Br-
t
3 . c C 3 H 7 C H 0 , RT 4 . H 2 / P d - C , MeOH
H
2!sH1 1
HNWNH 46%
*
Cristau, H.-J.*; Chiche, L. ; Plengt, F. SECTION 351: Amine n yr N-CH C 0 M e
*
I C g H 11
Synthesis, (1986), 56
-Ester 1 . LDA, THF, -30°C 2 . Me1 t
CO, Me
wPr--J-
3 . H30 , 2 0 ° C
NH, 8 2 % (82% ee)
Bajgrowicz, J.AZ; Cossec, B.; Pigiere, C.L.; Jacquier, R.; Viallefont, Ph. Tetrahedron E,(1983), 24, 3721
C H 2 =NOBn
PhCH=C,
,OTMS
C02Me
OM e
10% M e 3 S i O T f ,
CH2C12,
7h
RT
*
I
PhCHCH2NHOBn
Ikeda, K.: Achiwa, K.; Sekiya, M. Tetrahedron Lett, (19831,
93%
2, 4707
SECTION 351
-
AMINE
1 . Et30
t
-
BF4 ,
0°C t
CH2Ci
L
8 min)
2. HOH(tln
\
377
ESTER
t E t 0 2 C ( C H 2 ) 3 N H 3B
F4-
61 %
* Smith, M.B. ; Shroff, H.N.
J Org Chem, (1984)) 49, 2900 Tetraedmn E ,( 1 9 8 3 ) 7 2 4 , 2091
OTlilS
Et02C
C O E t
H
B nN ( CH 2 S Me )
\OTMSOEt
CH2C12,
C02Et
?
30°C
Bn
5h
68%
*
Miyazawa, S . : Ikeda, K.; Achiwa, K.; Sekiya, M. Chem Lett, ( 1 984), 785. -B nN,
,C02Me I
c =c
/ SiMe3
Me02C
C02Me
CH20Me
Me3S iO T f
Me02C
CsF,
THF,
*
Hosorni, A. ; Sakata, Y.; Sakurai, H.
*
1 . 0.1N HC1, RT,
2.
Gull, R.; SchBllkopf, U.
*
Chem Lett, (1984), 1117 THF
NH; HCI
60h
8N HC1,
3. EtOH,
Bn
60°C
reflux
reflux
Synthesis, (19851, 1052
4 3 7:
378 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 351
1 . LDA PhCH 2C02Me
2.
TMS-C1
3 . Py, PhN2+BF4-, 0°C 4. 5 a t m H2, Pd-C
Sakakura, T.; Tanaka, M.
*
DeShong, P. ; Kell, D.A.
C02Me
I
I C H CH CH
2 lN H B n
N I 02
EtCHC02Me
PhCHC02Me
73%
MeOH
*
JCS Chem Carm, (1985), 1309
: Sidler,
67%
D.R.
50, 2309
JOrg -.Chem, ( 1 9 8 9 ,
4 Et2CuLi, -6OoC,
Et20
3h
C02Me
1
*
E t C H C H CH
21
NHB n
7 0%
B a j g r o w i c z , J . A . ; El H a l l a o u r i , A . ;
V i a l l e f o n t , Ph.*
*
H; 2
J a c q u i e r , R.;
Tetrahedron, (19851, HC02-NH4 MeOH,
RT
t
,
10% Pd-C
P i g i e r e , Ch.;
5,1833
*
NH2
I
E t CH C 0 2 M e 67%
R a m , S.; Ehrenkaufer, R.E.
*
Synthesis, (1986), 133
SECTION 351
AMINE
1 . CH =C NCH2C02Et
-
.Me
, THF
'CH~OA~
P d ( d p p e ) , 2OoC
tl
2 . 10% HC1, RT
HC
379
ESTER
*
NH2 I C H = C H C H 2 C H C 02Me
50%
CI
Ferroud, D.;
NCH2C02Me
li
PhCPh
Genet, J . P .
x
: Kiolle,
R.
-
T e t r a h e d r o n Lett, (19861, 3, 23
1 , L D A , THF, -78°C
2. CH2=CHCH20Ac
Pd(dba)2,
DIOP
t
CH2=CHCH2CHC02Me 7 5%
3 . 1 0 % HC1
( 3 9 % ee R )
4 . K2C03 DIOP =
(42,5S-)-(t)-4,5-bis-(diphenylphosphinornethyl) 2,2-dimethyl-1,3-dioxolane
Genet, J.P.":
'NH-
Bn
Ferroud, D.; Juge, S.:
Montes, J . R .
T e t r a h e d r o n -.Lett, ( 1 9861,
3,4573
\
C O , MeOH, R T , 8h
Lathbury, D . ; Vernon, P . ; Gallagher, T .
N/I
~n
*
'
CO,Me
67%
Tetrahedron L e t t , (1 986), 2, 6009
Related Methods: A c i d - h i d e (Section 31 5 ) ; A c i d - h i n e (Section 316); h i d e - E s t e r (Section 344)
380 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 352: Amine
-
SECTION 352
Ether, Epoxide, Thioether
Br
c)JH , MeCN
I
CH2C=CH2
I
P d ( O A c ) 2 , 100°C
O C H 2 C H =CHCH3
*
O X N S 60%
Shi, L.; Narula, C.K.;
Me.
k
Mak, K.T.: Kao, L.: Xu, Y . ; Heck, R.F. J Org Chem, (19831, 48, 3894 ---
Me3SiC1,
PhH
iPr2NEt,
80°C
L O T M S Me
*
ih
6h
I t o , Y.*; Sawamura, M . ;
2o
96%
Kominami, K.: Saegusa, T. Tetrahedron E ,(19851,
0 2N e PhH,
N
HS Ph
RT,
1 5 min t
B F3 .OE t
26,
5303
CJ,sNp&02H
8 5% Benati, L . ; Montevecchi, P.C.; Spagnolo, P. Tetrahedron, (1986), 42, 1145
OCH20Bn
1. PhLi, -10
I
gC5H, CHCH=NNMe2
2. HOH
-
Et20 25°C
OCH20Bn
* "C5H1
I
CHCHNHNMe2
I
Ph
Claremon, D.A.
* ; Lumma,
*
( t h r e o : e r y t h r o = 98:2) 95% P.K.; P h i l l i p s , B.T. J Am Chem Soc, (1986), 8265 --.--
108,
SECTION 354
AMINE
SECTION 353: Amine
381
KETONE
-Halide, Sulfonate
iPrCHiN3 C1 ( C H 2 ) 4 M g B r
-
Et20,
iP r C H ( C
C1-
15°C-RT
57%
2h
Courtois, G . ; Miginiac, P..
i P r N C1 CH 3 C - C - C02 Me
I
LI
(19831, I1148
NiPr
NaOMe/MeOH
11 I
- 7
wrll Chem Soc Fr, ----
reflux,
II
w
1 .7h
CH~CCHCI
*
De K i m p e , N. ; Verhe, R . ; De Buyck, L.; Schamp, N. Tetrahedron Lett, ( 1 985),
83%
26, 2709
Review: "Reactions of B-HaloenarninesT1
*
De Kimpe, N. : Schamp, N. SECTION 354: Amine
Org Prep Proc Int, , -
-,
(19831, 9, 71
-Ketone
1 . TsN=S=O,
PhCH3,
2.
RT
5% NaOH,
3 . 5 % H C 1 , 0°C 4. 0sO4, N a I 0 4
O°C
w Me
71%
*
G a r i g i p a t i , R.S. ; Morton, J.A.;Weinreb, S.M. Tetrahedron Lett, ( 1 9831, 24, 987
-
382 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
FV P
t
(6OOOC) 1o
- ~t o r r
SECTION 354
t
*
60%
Gordon, H.J.; Martin, J . C . ; McNab, H. JCS Chan Carm, (19831, 957
---
0 II 1 . Me2C=CCCH3, E t 2 0 RT OE t
King, F.D.
2 . 2N H C 1
*
2,3281
Tetrahedron Lett, (19831, 1 .AlCl,
60%
&
, DCE
H
I
S02Ph
1 1 . BF3'0Et2,
2 . OH-,
* Kakushima, M . ; Hamel,
Q t
Y H 2 ?Me
DCE:,
dioxane
92%
Q-t H
64% P . ; Frenette, R.; Rokach, J. -J Org Chem, (1983) , 48, 321 4
n C 6 H 1 3CH0
>
d 0
n C 6 H 13
PhH, r e f l u x CH2-CCH=CH2 95% OMe Overman, L.E. ; Kakimoto, M . ; Okamki, M.E.; Meier, C.P. J Am Chem Soc, (19831, 105, 6622 ----
SECTION 354
-
AMINE
383
KETONE
NMe2, L i C 1 0 4
e
,
rotating disk
electrodes
Renaud, R.N.
Q
Matsumoto,
0 Me
* ; B&&,
,
MeCN
D.; Stephens, C . J . Can J (19831,
e,
CH2(NMe2)2,
MeOH
"high pressure, RT,
58%
61,1379
&NMe2
KBar" 53%
24h
* K . : Hashimoto,
S.; Otani, S . : Amita, F.; Osugi, J.
Syn Camnun, (19841, fi, 585 --
0 I1 1 . BrCH2CCH=CHPh Et20,
2. NEt3,
24h
*
PPh3
CH2C12, 3. LiA1H4,
U
2h Et20
Me
A
P
78%
-
Ghi rlando Y R . ;
0
Howard, A.S.*; Katz, R.B .; Michael, J . P . Tetrahedron, ( 1984), 40, 2879 1 . L D A , THF,
*
-78OC
2 . Me3SiC1 3. MeLi,
h
THF/Et20
* Me0
4. MeOQFH-N3 OTiCl
J
73%
Seebach, D.*; Betschart, C.: Schiess, M. Helv Chim Acta, ( 1984) , 3, 1593
---
384 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 354
( -exo:endo = 4 . 2 : l ) * Grieco, P . A . ; Larsen, S.D.; Fobare, W.F. Tetrahedron Lett, (19861, 3,1975 1. nBu3SnCH2NEt
0
0
It
Me2CHCC1
-
2 2OoC, 1 5 m i n
2 . 3N H C 1
*
0
II
Me2CHCCH2NEt2
3 . 3N NaOH
64%
Verlhac, J.-B. ; Quintard, J.-P.
Tetrahedron Lett, (1986),
h\C/NH P h
1 . P h M e C = N P h , A1C13 d i o x a n e , 100°C
I1
CH CI = N H
Ph’ Barluenga,
2. LiA1H4, 3 . H30t
* J. ; Cuervo,
Satoh, T.; Kaneko, Y . ;
THF
2,2361
PhCHNH P h
I
*
FH2
cI =o Ph
56%
H.; Olano, B . ; Fustero, S.; Gotor, V.
Synthesis, (1986), 469
* K.
Sakata, K . ; Yamakawa, Bull Chem Soc Jpl, (19861,
----
97%
2,457
SECTION 355
AMINE
-
3 85
NITRILE
fl:: eH
Amine - Nitrile -.SECTION 355: -
17
P Ph SB Su P3 ,h T H F
N-OH
Barton, D.H.R.;
H,N
Simon, E.S.: Zard, S.Z. JCS -.Chem -.C a m , (19841, 337
-
Zn12
15 min
3CH0
tN
-6
Fife, W.K.
*
TMS-CN,
-7°C
Me2NiC1, C H 2 C 1
I
t
83%
25, 4583
>a+ 0 ' \
N
CN
NC
Heterocycles, (19&4), 22, 93, 1121 1 . TMS-CN
PhCH =CHCH=NPh
Prajapati, D.;
nC6H1 3 C H N H 2
( 96
0
2. l h b r u s h , R.C.;
*
CN
2 . N H 3 , MeOH 4 0 ° C . 2h * Mai, K . ; Patil, G. Tetrahedron Lett, (19841,
0
y i eI d '
CN
Motherwell, W.B.;
1 . TMS-CN, nC6H1
' good
2 . AcOH NaCN
AcO
*
Sandhu, J.S.
N
4)
95%
CN
I
PhCH =CHCHNHPh
* ; Baruah,
90% J.N.
Ind J Chem B y ( 1 984), 23, 853 ----
386 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CN I P h C H O T M S , MeOH
Me
r e f l u x , 2h
Ph
*
Mai, K . ; P a t i l , G.
Me t
It
CH3CCH3
*
Mai, K . ; P a t i l , G.
=
Syn Carmu, (19841,
2 . RT, TMS-CN 3 . lOO"C, 1 min 4. R T Syn -Ufly
H Ph
(RR:RS
1 . BnNH2, neat lOO"C, 1 min
0
SECTION 355
CN Ph
97%
3:l)
e,1299 CN
I
>
CH3CNHBn
I
CH 3
97%
(1985)s 15, 157 Inti',( 1985) , 2,183
Org P r e p Pnx: -
1 . t B u M e 2 S i O T f , CH2C1 2 , 0°C 2. M e L i , T H F , 0°C 3. CH2C12, TiC14 - 7 8 " C , 30 m i n 4. T M S - C N , -78°C-RT 5. a q . NaOH
-0
Tokitoh, N . ;
O k a z a k i , R.
W N CN , M@
w
63%
Chem L e t t , (1985), 241
1 . P s S e S e P h , NaCN AcOH, 5 d , 2OoC
H Barton, D.H.R.
*
*
2. a q . NaOH ; B i l l i o n , A.; B o i v i n , J. T e t r a h e d r o n -.Lett, (1 985),
H
95%
26,
1229
AMINE - OLEFIN
SECTION 356
387
SECTION 356: Amine - Olel'in - -
CH2=CHBr, 100°C H
4
P ~ ( O A C ) ~ ,P ( g T o 1 )3 CH2=CHCH(OMe)2
OMe
C / , d O M e
~
57%
F i s c h e t t i , W.; Mtk, K.T. ; Stakem, F.G.; K i m , J.-I.; R h e i n g o l d , A.L.; Heck, R.F. -J Org Chem, (19831, 48, 948
Br
I
I
CH2=CCH2CH2CH2CH=CH2 H
Narula, C.K.:
Pd(OAc)2, P(oTo1 ) 3 1 0 0 ° C , 66h
Mak, K.T.:
CH2=C=CH(CH2)3NHPr
Heck,
71 %
* R.F.
--J Org Chem, (19831, 48,
2792
ASB Fq
P
dioxane ref1 ux
a-Pr
95%
Tetrahedron .-Lett, (19831, 2 2 , 3997
A r s e n i y a d i s , S . ; Gore, J.
o +Vp-s, gu 6;;; P d ( O A c )2
CH2=C=CHnBu
dPPe
______)
:::*r
Shimizu, I . ; T s u j i , J.
ux
-Chem L e t t ,
Ph ( 3
:
(19841, 233
I ) Ph
65%
388 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
*
SECTION 356
7 5%
z, (19841, 25, 4437
Tamura, R. ; Hayashi, K . ; Kai, Y . ; Oda, D.
Tetrahedron
0""'
1 . CuCN 2.
Ishikura, M . ; Kamada,
*
CH2=CHCH2Br
* M . ; Oda, I. ; Termhima, M. Heterocycles, ( 1 985), 3
6 9%
117
: Termhima, M. Heterocycles, ( 1 984 1 , 22, 2475
Ishikura, M.; Kamada, M.; Ohta, T.
CF3COOH, CH3CN,
Overman, L.E.
* ; Burk,
2h
82°C
H H
90%
R.M.
Tetrahedron
Lett, (19841, 25, 5739
C HCHO F3COOH Me3SiCH2CH=CHCH2CH2NHBn
-3 Y
Bn
a q . T H F , RT
Grieco, P.A.
* ; Fobare,
56h
W.F.
Tetrahedron L e t t , (19861,
81 %
3, 5067
SECTION 356
-
AMIFlE
1. nBuLi,
hexane
reflux,
20h
2. I-PhCH=CHBr, PPh MeLi, 3 . a q . 3 i H C1
Murahashi , S.-I. ; Naota, A
389
OLEFIN
PdCl PhH,
* reflux
*
4.. ; Tanigawa, Y . -Org Syn, (19841, 62, 39 n
67%
Me2C=CH ) 2 C u L i t (OMe
Et20, r e f l u x
GO% Germon, C . ; Alexakis, A . ; Normant, J.F. B u l l Chem Soc Fr, (19841, I1377 -,--I. CH3CH=CHCH0
OH-HCI, KCN
HOH, 2.
*
EtMgBr,
0°C-RT THF,
0°C-RT
ANbrecht, H. ; Dollinger, H.
Synthesis, (19851, 743 t
[ R h - ( R - b in a p ) , ] C l
+NR2
120"C,
>
3h
78%
O4 - T p N E t 2
18h
(100% ee S )
binap
*
Tani, K . ; Yamagata, T.; Tatsuno, Y.: Yamagata, Y.: Tmita, K . ; Akutagawa, S.; Kmobayashi, H.: Otsuka, S. Chem Int Ed Engl, (1985), 24, 217 ---
-
390 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
PhNH2,
HgC12-K2C03
THF-HOH,
Barluenga,
* J. ; Aznar, 1. TiC14,
SECTION 356
7OoC I
Ph
F.; Liz, R . ; Cabal, M.-P. JCS -.Cheg Ccmn, (1985), 1375
-
-
5h
NH-B n
NH-B n
NB n - 7 8 O C SnBu3 RT, Keck, G.E.*:
78%
l h
-J Org
Enholm, E . J .
TMS
h e d - S c h o f i e l d , R.:
' Me
1)
(23
(19851,
C-,
* P.S.
CH2=CHCH 2SnMe3 ho, MeOH t
Berg, R.M.:
Mariano, P.S.
50,
15%
5667
Qy Me
*
146
TMS
60%
Mariano, -J Org C k a , (19851,
c104-
50,
-
\
71%
Tetrahedron Lett, (19861,
3, 2821
SECTION 356
-
AMINE
391
OLEFIN
1 . MeCH=CHCH2-B Et20,
PhCH =NPh
*
ye
-78°C
2 . HC1, 0°C 3 . a q . NaOH,
-
Phy=V,
>
NHPh
RT O°C
93%
YamamOto, Y. ; Komatsu, T.: Muruyama, K. J Org C-, (1985), CH2=CHCH20H,
50,
1 2 0 - 1 50°C
t
PhNH2
P t C l 2( P P h 3 ) 2 - S n C 1 2 - 2 H 2 0
CH2=CHCH2NHPh
Tsuji, Y.: Takeuchi, R . ; Ogawa, H.; Watanabe, Y.
-Chem L e t t ,
NPh
CH2=CHCH2SnBu3,
II
PhCCl
3115
PdC12(PPh3)2,
67%
*
(1986), 293
PhH
120°C
NPh
t
II
PhCCH =CHCH
8 6 7;
1 Oh
*
*
Kosugi, M. ; Koshiba, M.: Atoh, A . : Sano, H.; Migita, T. Bull C b -.Soc (1986), 2,677
s,
CH * 0 S 0 2 M e I
TKSCH2C =CH PhCH=NPh Ni[P(OEt)3]4,
PhCH3
reflux, overnight
Jones, M.D.;
Kemitt, R.D.W.
*
b\
Ph
Ph
77%
JCS C k m colea, (1986), 1201
392 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
T r o s t , B.M.
* ; Chen,
S.-F.
SECTION 357
s,
J Am Chem Soc, (19861, . 6053 SPh
C H 2CH *N3
CHC13,
I
CH =CCH =CH2 I
SPh
Pearson, W.H. Glens, J . H .
* ; Celebuski,
70°C 3d
L W
62%
Poon, Y.-F.;
J.E.;
/-A
*
Dixon, B.R.;
-
Tetrahedron Lett, (1 9861,
Reviews:
2,6301
"Diels Alder Reactions of Azadienes" Boger, D.L.
*
Tetrqhedron, (19831, 39, 2869
ttSynthesis of Primary A l l y l i c Aminesll Cheikh, R.B.;
Choabouni, R . ; Lament, A , ; Mison, P . ; N a f t i , A . Synthesis, ( 1 983 1 , 685
"Recent Advances i n t h e Chemistry of Conjugated Enmines" Hickmott, P.W.
*
Tetrahedron, (19841,
SECTION 357: Ester
C.W.
*;
2989
-Ester 1 . Pb(OAc)4,
Rubottom, ( Y O S i M eG.M. 3
40,
CH2C12
R T , 3 0 rnin 2 . E t 3 N H F , RT Gruber, 3.M.; Marrero, R.:
J Org ---
Juve J r . , H.D.;
Chem, (19831, 48, 4940
66% Kim,
SECTION 357
ESTER
0
P h CCH 2 C H 2 C O O H
HC(OMe)3, H O H
* ; Peterson,
82%
4h
7 9%
2,1469
Tetrahedron, (19841,
J.R.
E n 3 ( OAc ) 7 AcOH,
40°C
24h
* ; Kang,
64%
M.
---J Am Chem
Soc, (19841,
1 . LDA, - 7 8 ° C THF/HMPA
2 . MeCH=CHC02Et -78OC
Yamaguchi, M.*:
PhCHCH *C02Me
-
'OH
nPrC02Et -
I
t
R.A. ; Katz, A.H.; McKillop, A.H. -J Org Chem, (19841, 9, 3840
4 0'
Corey, E.J.
C02Me
2.8h
* : Conley,
Fristad, W.E.
3 93
ESTER
T1 ( N 0 3 ) 3 * 3 H 2 0
II
Taylor, E.C.
-
3 . a q . NH4C1
Me
+
Et+,
CO,Et C0,Et
(20
106,5384 ye E t p , 'OFt
C02Et
1)
a7 % Tsukamoto, M.; Tanaka, S.: Hirao, I. Tetrahedron E ,( 1 9841, 25, 5661
394 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
"
Bn
,>\+--(
0 . 1 PdC12,
OH
Hood t
CO,
AcOH,
NaOAc,
I d
bo
3 CuC12 RT
SECTION 357
*
0-
0 : Me
84%
*
Tmaru , Y.; Higashimura, H.; Naka, K.; Hojo, M.; Yoshida, Z. Angew Chem Int Ed 9,( 1 985), 2,1045 ---I-
0
Mn30(0Ac)7,
AcOH t
3 . 5 H02CCH2C02Et 23OC
* Corey, E.J. ; Gross, A.W.
7 5%
-
Tetrahedron Lett, (1985),
26,
4291
THF - 1 00°C
CO, Me
Z-MeCH =CHC02Me
54%
(erythro:threo = 75:25)
* Corey, E.J. ; Peterson, R.T.
-
Tetrahedron Lett, (1 9851,
Me0 C C H C 0 Me
PhCH3, MeOH,
26,
CO,Me
CAN
RT
5025
*
&,Me
5 9%
(2:m:p = 5 1 : 2 1 : 2 8 ) Baciocchi, E.*; Dell'aira, D.; Ruzziconi, R.
-
Tetrahedron Lett, (19861, 27, 2763
ESTER
SECTION 358
0
ETHER
1 . S m 1 2 , T H F , O°C
0
II
-
II
HC(CH2)40CCHCH3 I Br
395
0
2. A c 2 0 , D M A P
82%
Tabuchi, T.; Kawamura, K.;
Inanaga, J.*: Yamaguchi, M. Tetrahedron Lett, ( 1 986), 3, 3889
Also via: Dicarboxylic acids (Section 31 2 ) ; Hydroxyesters (Section 327; Diols (Section 323) SECTION
358:
Ester
- Ether,
Epoxide, Thioether
CH CH COOH
l 2
cat. HgO
C
111 * L
\
( C H 2 )30H
DMF,
*
reflux
73%
2h
Yamamoto, M. ; Yoshitake, M.: Yamada, K . JCS -.Chem C a m , (19831, 991
-
-
5 CH2=C(OMe)2 PhCH3, llO°C 15h Boger, D.L.
i
; Mullican,
M.D.
Tetrahedron E,(1983),
86%
2, 4939
396 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 358
:H2CO2Et C02Et
*
o*o
Ac20,
K
A.D.
oA
AcO
c a t , H2S04
RT, 1 0 h
* W.F. : Rivera,
83%
--Bull Chem Soc a, (19831, 5, 1428
: Takeuchi , R.
Watanabe, Y . ; T s u j i , Y .
Ph
u
oAo
12OoC, 6h
C02Et
Bailey,
CHC02Et
*
OAc
*)i
96%
J Org Chem, (19841,
9, 4958
H 2 N B S , CC14 22"C,
*
2h
C H 2 C H 2 C H 20H
Williams, D.R.
/ OTMS
65%
* ; Harigaya, Y . ; Moore, J.L.; D'sa, A. J Am Chem SOC, (1984), 106,2641 ---0 II
PhCCH3,
50°C
MeCH =C. \
(L) O E t
Yamamoto,
1 0 KBar,
* Y . ; Maruyama, K . ;
OTMS
*
I
PhCHCHC02Et
6d
I
Me
85%
( e r y t h r o : t h r e o = 55:45)
Matsumoto, K . Tetrahedron Lett ( 1 984),
-
25, 1075
SECTION 358
ESTER
Me
-
397
ETHER
-
I>- k - 0 S i M e 2 t B u I
PhCH=CHC02Me
/ 0\
OOCPh
II
0
Pd(OAc)2,
CH2C12,
Nagata, R . ; Matsuura, T.; Saito,
PhCH -CHC02Me
8h
* I.
59%
Tetrahedron Lett, ( 1984) ,
1. COY CBuLi,
25, 2691
-110°C
TH F / p e n t a n e / E t 2 O 2.
C O Y 2h,
-110'C-RT
3 . Me1
5 5%
*
Seyferth, D. ; Hui, R.C.
Organmetallics, (1984),
t
1 . Fle2S-SMe B F 4 MeCN,
2.
RT,
O'Malley, G . J . ;
*&
-
30 min
iPr2NEt,
MeCN
'5
36h
Cava, M.P.
x, 'CHO
Tetrahedron Lett, (1985), 26, 6159
*
5% Zn12,
Kita, Y . ; Yasuda, H.; Y.
S Me
86%
*
.OS it 4 e 2 t B u C H =C 'OMe
0
2, 327
MeCN,
-
48h
c
C
0
2
M6 7 e%
OSiMeetBu RT ( a n t i : s y n = 96:4) Tamura, 0 . ; Itoh, F . ; Ke, Y.Y.; Tamura,
O0C
-
Tetrahedron
E ,(
398 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 358
OTMS
I 1C5H1
CH2C12, 20°C
CHCHO
t
2 . Py
B n w C O z E “‘gH1 1
*
*
Oshino, H.; Nakamura, E. ; Kuwajima, I. -J Org C h e ~ , ( 1 985), 0 II E t O Z C C H 2 S M e , CH2C1 SnC14,
Stamos, I . K .
*
Murota,
0°C
-
RT
* K . ; Matsuda,
A.:
50, 2802
&&
Tetrahedron L e t t , (19851,
CO/HOH, 5h
93%
MeSCHCOZEt
95%
26, 477
C O ~ ( C O ) ~ y, - p i c 0 1 i n e
MeOCHzOMe
OSiMe3
MeOH, 1 6 0 ° C
t
MeOCH2C02Me
(65% conversion)
Masuda, T.
--will Cheto S o c a ,
(19851,
50%
58,
2141
l
~
PdClZ, CuC12 A c O N a , AcOH OH
OH
Tamaru, Y.;,Kobayashi, Yoshida, Z.
CO,
RT,
t P
h
Id
80%
T.; Kawamura, S.; Ochiai, H.; Hojo, M.; Tetrahedron Lett; (1985),
26,
3207
~
o
ESTER - ETHER
SECTION 358
0 II PhCS-SePh,
399
0 II
AIEN
PhH, r e f l u x ,
“3 ePh
17h
54% E, 1 0 % I * Toru, T. ; Seko, T.; Maekawa, E. Tetrahedron Lett, ( 1 985), 26, 3263 0
\
STol
6
Marino, J . P .
*
STol
2 . Al(Hg),
a q . THF
; De l a Pradilla, R.F.
Tetrahedron E ,( 1 985),
68%
26, 5381 Me
______)
AcOH ,
Ferroz, H.M.C. Zocher, D.H.T.
* : Brocksm.
Pinto, A.C.:
Tetrahedron 0 II PhCCl
Abla, M.A.:
s, (19861,
3, 81 1
, NEt3/MeCN
OOC-RT,
Hormi, O.E.O.;
T.J.:
85%
N a m a n , J.H.
12h
*
Carmun, (1986),
61 %
16,69
400
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
S EXXION 359: Ester ---
C02Et
-Halide, Sulfonate C02Et
NaH, T H F , - 2 0 ° C
I
PhCHC02Et
Barnette, W.E.
*
SECTION 359
~ T o SlO 2 - NI
I
>
A
PhC-C02E t
I
F
F
J Am Chem Soc, (1984), ----
81 %
3,452
I
I
85% T q a r u , Y . ; Mizutani , M. ; Furukawa, Y ; Kawamwa, S. ; Yoshida, Z . ; Yanagi, K . ; Minobe, M. ---J Am Chem Soc, (19841, 3,1079
.
0
I1
E t 2 N S F 3 , 0°C
PhCCH2CH2COOH
Patrick, T.B.
CHC13, 3 0 m i n
* ; Poon,
* 85%
Tetrahedron=,
Y.F.
PhN2
+
C1
- ,
KI
C H =CHC02Me
*
(19841,
25, 1019
I
I
PhCH2CHC02Me
E t O H , 30"C, 3 0 m i n Ganushchak, N . I . ;
Obushak, N.D.;
Polishchuk, O.P.
---J Org Chem USSR,
(19841,
g,595
45%
-
ESTER
SECTION 360
1 . C12, CC14,
2 . Bu4NC1,
401
KETONE
MeCN
RT,
8h
3. a q . H202
Morella, A.M.;
*
Ward, A.D.
82%
Tetrahedron Lett, ( 1 985), KF,
26,
2899
CH2Br I
reflux
8h
Anzeveno, P.B.
CI
*;
Campbell, J . A . ; White, W.L. Syn Cornnun, (19861,
QCN
1 .MeCN,
2.
2-r
CN Robert, A.
*.
97%
NaOCl
16, 387
CI
pH 5 - 6 48% H B r
iPrOH,
reflux,
3h
Jaguelin, S. : Cuinamant , J . L . Tetrahedron, (19861,
0
2,2275
8 3%
Also via: haloacids (Section 31 9) ; Halohydrins (Section 329)
SECTION 360: Ester
CH2=C
/Me
\
Ketone e-,
1. EtNO2, cat,
C02Me 2 .
Monte, W.T.;
-
MeCN
PhN=NPh,
-
Bu4NBr
e , MeCN 0 2 ’ Bu4NBr
Baizer, M.M.;
*
L i t t l e , R.D. (19831,
-J Org Chem,
li
rH3 CH3CCH2cHCO2Me
60%
2, 803
402 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
c1
OTMS
I
1 . PhSLHCO2Me,
PhC=CH2
L e e , T.V.
1 . TiC14/CH2C12
Fleming,
* I. ; Iqbal,
6
Me0
0 ZnBr2
2. Ni/H2
* ; Okonkwo,
2.
92%
(19831, g,323 73%
Tetrahedron E ,(1983), 2,327
J.
1 . BrZnCH2C02Me
2 . CAN
Pearson, A.J.
* ; Richards, 1.
-nC5H, CCH3
It
PhCCH2CH2C02Me
Ni(R)
F e ( C 0 I 3 PF6-
-8
C02Me
9 0%
I.C.
Tetrahedron Lett, (19831, 2,2465
&CH20Me Y NH2 THF,
2.
LDA,
-78°C
3.
PhCH=CHC02Me
4 . 0 3 , CH2C12,
Enders, D.
p
Tetrahedron=,
J.O.
SECTION 360
t 59%
-78OC
C 0 2- M e
* : Papadopoulos,
K. Tetrahedron Lett, (1983), 24, 4967
86%
Mander, L.N.: Sethi, S.P.
Tetrahedron Lett, (19831, 2, 5425
ESTER
SECTION 360
KETONE
-
1 . base, CH2=CHCCH3
0
I '
II
*
403
THF, 20°C CH,C(CH,),CH(CH,),CO,Me 2 . M e O H / N a O M e , 0°C 3. AcOH 93% Huggenberg, W.;
Hesse, M.
* --Helv Chim Acta,
0II 0II 2C8H1 7C-C-COR
*
Rh2(0Ac)4,
L
R* = Taber, D.F.
&I K.
MeOH, RT 24h
* -J Org Chem, E.
MeHN Me
&C02R*
*
105, 5935 OMe
I
P h - CI - C 0 2 M e I
OMe
71 % (19841, 3,515
yo-Na+ 'Ph
T H F , O'C,
* R.O. : Maienfisch,
4h
1519
60%
J Am Chem Soc, (1983),
1 2 ' 5 1205
Cohen, M.J.: McNelis,
66,
"V
a - n a ph t h y 1
Ph C E C C 0 H
Duthaler.
~
CH2C1
* ; Raman,
&
RT
(19831,
* (81% e e R )
P. Helv Chim Acta, ( 1 984) , ---
60%
3, 845
SECTION 360
404 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1.
EtO,
,OTMS
TMso/c=c'
OEt
CH2C12, 4 5 m i n
2 . MeOH,
61
, ZnC12
2N HC1,
RT
*
CC02Et
5 min
84%
Reetz, M.T.*; Heimbach, H.; Schwellnus, K. Tetrahedron Lett, (19841, 25, 51 1 1 . iPrfHCH20H,
0
It
PhCCH2C02H
2.
NH2 LDA, M e I ,
3.
LDA,
t
THF,
BnBr,
4. nBuOH,
heat -78°C
-8O"C,
1 0 % H2S04
reflux,
>
THF
PhC-C-CO2FBu I
Me
(S)
96h
50%
Meyers, A.I. ; Harre, M.; Garland, R. J Am Chem Soc, (19841, 106,1146 ----
\
0 U
1 . PhCHO, E u ( f o d ) 3 CH2C1
4
57%
Castellino, S.; Sims, J.J.
Tetrahedron Lett, (1984), 25, 2307
1 . LDA, EtC02CH2C02Et 2 . H30+ t
0°C
*
0
II
EtCCHC02Et I
OH 57%
Lee, S.D.: Chan, T.H. ; Kwon, K.S. Tetrahedron Lett, (19841, 25, 3399
SECTION 360
1
.
405
KETONE
(MeO) 2PCH, ,C02CMe2CC1 3 C02Me
L iN ( TMS )
nBuCHO
-
ESTER
2 . Z n ( d u s t ) , 25°C 3. HOH
0
I1
0°C
nBuCC02Me 66%
*
Horne, D . ; Gaudino, J.: Thompson, W.J. Tetrahedron Lett, (19841,
0
II
CH3CCHC02Me
I
Me
2 CH2=CHCH20Ac, 20°C nBu3P, THF
*
5% R h H ( P P h 3 ) 4
*
25,
Me I
93%
Tetrahedron Lett, (19841,
25,
5157
PhH
reflux, 21h Dunlap, N.K.:
&
C02Et
Sabol, M.R.:
*
Watt, D.S. Tetrahedron E ,(19841,
84%
3, 5839
(TMS)2S04 DCE,
80°C
~
Me
lh
(65
*
Morizawa, Y . ; Hiyama, T. ; Oshima, K.: Nozaki, H. Bull Chem Soc Jpn, (19841,
----
0
II
CH2=CHCH2-C-CMe I C02Me
T s u j i , J. ; Minami, I . ; Shirnizu, I.
Mn(OAo)3,
3529
35)
71 %
57, 1123
406 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
-
A C 0 2 E t
U
Pinkey,
Me
\
OMe
NPh CN
82%
* J.T.
1 . Me2C=C,
l
CH =C
t
24h
Kozyrod, R . P . ;
/
%
M e O e P b ( O A c ) 3 PyICHC13, 40°C
Org Syn, (1984),62, 24
10-
*
H30
1.
it
Me2CHCC1
THF
EtO, TMS 0
-78°C
,c=c,
S.-H.
1 . KH, C02Me
,OTMS
,
OEt 22"C,
0 II Me2CHCCC02Et I1 0 93%
ZnC12
4h
t
Tetrahedron Lett, (19851,26, 6333 DMSO,
2. Me2C(N02)2, 6h
*
Me
Synthesis, (1985), 417
2. Ht
Reetz, M.T.
I
CH3CCH2-f'-C02Me
%
7 9%
CH2C12,
* ; Kyung,
Me
Ii
t
Ahlbrecht, H. ; Dietz, M.
0
,
OMe
-78°C 2 . M e I , THF, 3.
SECTION 360
0
15 min DMSO
C02Me
? & o * 86%
Kornblun, N. ; Kelly, W.J.; Kestner, M.M. --J Org Chem, (1985), 50, 4720
SECTION 360
-
ESTER
1 . LiA1H4,
THF
407
KETONE
0
*
2 . HC1, d i o x a n e
0
II
II
P hCH 2 C O C H 2 0 C P h
Ph
Naim, S.S.; Hussain, M.; Khan, N.H.
t'"u C02Me
2 Mn(OAc)3, 60°C,
64%
*
Synthesis, (19851, 48
AcOH
CU(OAC)~ l h
-pr
C02Me
"%,,
75%
*
Snider, B.B. ; Mohan, R.: Kates, S.A. --J Org Chem, ( 1 9851, 50, 3659 P d C l 2( P P h 3 ) 2 ,
*ae
MeOH
NEt3,
600 psi C O
MeCN,
PhH,
24h
100°C(autoclave)
Tour, J.M.; Negishi, E. 0
C
0 II OCPh
CGCH
1.
* 2 Am
II
(PhC)20, CH,Cl,,
2 . O°C 3.
-
pH 7
Tanabe, Y.; Mukaiyama, T.
Chem SOC, (19851,
Ti(OTfI2 O°C
RT
84%
107, 8289
0 II -0CPh
C
C C H CPh II 2 II 0 0
Chem Lett, (19851, 673
87%
408 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. Zn/Cu,
I CH 2CH 2 C 0 2 E t
RT
Me2NAc,
-
PhH
SECTION 360
0
II
6OoC
EtCCH2CH2C02Et
2. Pd(PPh3)4, 5h 3 . CH CH C C 1 , 3 0 m i n 3 211 0
84%
Tamaru, Y.: Ochiai, h.; Nakamura, T.: Tsubaki, K.; Yoshida, Z. Tetrahedron Lett, (1985), 26, 5559 1. (cBu3Sn)20
2 PhCH2COOH
*
0
0
P h ! O C H 2 : o B r
2 . BrCH C o B r 211 -
0
60%
Vijayaraghavan, S.T.; Balasubramanian, T.R. -J Organofnet Chem, (1985), 282, 17
Os04, L B u O O H
PhCsCSiMe3
MeOH
0
It
t
PhCC02Me 61 %
Page, P.C.B.*; Rosenthal, S. Tetrahedron Lett, (1986), 3, 1947 1 . 2 Ph3P=CHC02Et
0
II
PhH,
EtOCH2CH2CC1
5OC-RT1 2 h
2. Al(Hg),
*
w e t THF
0
II
t EtCH2CH2CCH2C02Et 87%
Shchez, I .H. ; Larraza, M.I.; BreGa, F.K. ; Criiz, A. ; Sotelo, 0.; Flores, H.J. Couunm, (1986), 16,299
SECTION 361
ESTER
l o PhC, E t
100°C,
C-CH(CM2)4CH3
w
EtCCHnC5H1
I -
H
2
N
OAc
*
84%
Yamakawa, K . will Chem Soc Jpn, (19861, 59, 946 ----
n ii
t
C
DMSO
2 . a q . HC1
Satoh, T.; Motohashi, S.:
e
409
NITRILE
1 . CsOAc/Pb(OAc)4
/ \
/
-
M- e 3 0,CPh
II
PhCOCH 2 C P h
L
Thorat, M.: Mane, R.; Jagdale, M.; Salunkhe, M. Org Prep -Pnx? I n t , (1986), PhI, CO, CH3CH ( C 0 2 E t ) 2
Kobayashi, T.: Tanaka, M.
99%
2,203
;
12OoC, N E t 3
PdC12(dppf),
i
0
*
PhCCH2Br EtOH, 2h
y 2 E t PhC-C-CO2Et
33h
I
Me 75%
*
Tetrahedron Lett, (19861,
3, 4745
ec
Also via: Ketoacids (Section 320); Hydroxyketones (Section 330)
SECTION 361: Ester
CN OH
-
Nitrile
1 . LDA, 0
THF
- 2OoC, 12h
2 . A c O H-7OOC , THF
*
*
Milenkov, B.; Siisse, M . ; Hesse, M. Helv Chim Acta, (1983), ---
68,
51 %
21 15
410 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 362
1 . KOH/EtOH
E m s t , A.B.:
Fristad, W.E.
50%
*
8%
-
-
Tetrahedron Lett, (1985), 26, 3761 CN
PhBr,
NECCH C 0 E t
Uno, M.;
LBuOK,
PdC12(PPh3)2,
5h 70°C
I
b
PhCHC02Et
7 3%
monoglyme Ueda, W.: Masuda, M . ;
Seto, K.;
Takahashi, S. Synthesis, (19851, 506
SECTION 362: Ester
-Olefin
This section contains syntheses of enol e s t e r s and e s t e r s of unsaturated acids.
, I
Shea, K . J . ;
E
4h Gilman, J.W.
Me2C=CHCH20H
Vatele, J.-M.
*
Tetrahedron Lett, (1983), 3, 657
1 . KH 2.
^.
85%
F, c, = c, .Me Me0 S(O)Pi7
* 60°C
CH 2 = C - C 0 2 M e
I
M e - CCH = C H 2
Tetrahedron Lett, (19831, 24, 1239
I
Me
65%
SECTION 362
ESTER
-
t -
n B u 2 T e - C H C 0 2 E t , THF PhCHO -2OoC,
41 1
OLEFIN
l h
*
PhCH=CHC02Et
(E:I =* 5 0 : l )
*
75%
Osuka, A. ; Mori, Y.; Shimizu, H.; Suzuki, H. Tetrahedron =,(1983) , g!, 2599
Na2S, B~ Br
cat.
PhH/HOH (C8H17)3NMeC1 l h
88%
* Nakayama, J. ; Machida, H.:
Hoshino, M. Tetrahedron E,(1983) , 2, 3001
Aryal-Kaloustian, S . : Agosta, W.C. --J Org Chm, (19831,
48,
1718
81 % 1)
412
CI
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
NOz
SECTION 362
1. NaC(Et)(C02Et)2 HMPA
2 . NaBr,
,
hw
140"C,
3h 56%
*
Ono, N. ; Tamura, R . 4 Eto, H i ; Hamamoto, I . : Nakatsuka, T.; Hayami, J . ; K a j i , A. --J Org Chem, (1983), 48, 3674
,
1.
Ti(3iPr)4,
2 . LiAlH,,
boo
TiC14 -20°C
Et,O
25°C S 0 2 N iP r 2
3 . Cr03,
84%
a q . HC1
(88% ee R )
*
Oppolzer, W. ; Chapuis, C . ; Kelly, M.J. Helv Chim Acta, (19831, 66, 2358 Oppolzer, W.*' Chapuis, C - T m z n L e t t , (1%4), 3,5383 Oppolzer, W.": Chapuis, C . ; B e r n a r d i n e l l i , G. Tetrahedron Lett, (1 984) , 25, 5885
-
TMS-CH2CCH20Ac
nC 6 H 1 3 C H =CH C02Me (E)
dppe,
THF
P c ~ ( P P ~ ~ ) ~ , r e f 1 ux
Trost, B.M.*; Chan, D.M.T. T r o s t , B.M.
C02Me 51 %
---J Am Chem SOC, (1983), 105, 2315, 2326 * ; Balkovec, J.M.; Angle, S.R. Tetrahedron Lett, (1986), 27, 1445
SECTION 362
ESTER
Q
-
413
OLEFIN
Li I
&
C02Et
1 . Me2CC02Et, 8 p s i C O THF-HMPA, -78 25°C
-
2.
EtOS02F, - 7 8
-
25°C
"'C 0 E t
Fe ( C O ) 3
96%
a*
*
Semmelhack, M.F. ; Herndon, J.W.; Springer, J.P. J Am Chem Soc, ( 1 983), 105, 2497 ----
0,
0 II R OCCH=CH2
*
TiC12(0iPr)2
C02R
O C H 2t-B u
Oppolzer, W.
x
* : Chapuis, 1.
C.; Dupuis, D.: Cuo, M. Helv Chim Acta, (1983),
---
2100
C =Cr ( C O ) CH2=CH
PhH,
I
25"C, 1 .5h
C02Me
2 . D M S O , 3 . 5 h , 25°C
*
0
I1
68,
MeO,
Wulff, W.D. ; Yang, D.C.
PhCH=CHCH20COMe
Trost, B.M.
91 %
J Am Chem ----
71 % Soc, (19831,
NaCH(C02Me)2, T H F T H F , 1 5 % bpy 1 5 % (MeCN),W(CO), 4h
* ; Hung, M.-H.
J Am Chem Soc, ----
*
105,6726 CH=CH2
I
PhCHCHC02Me
I
C02Me
(19831,
105,
7757
91 %
SECTION 362
414 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. secBuLi, THF TMEDA, -78°C
0
II
CH3CH=CCNHMe
I
0 0 , THF -78°C-RT 3 . pH,3, r e f l u x Pattenden, G. Syn Commrn, (19841,
2*
CH3 Ladlow, M.;
4 0%
2,11
0 II
Et02CCC02Et, 180°C sealed tube, 72h Salornan, M.F.:
90%
* G.
Pardo, S.N.; Salornan, R 49, 2446 --J Org Chem, ( 9841, n
1 . MeLi, T H F , 1 . 5
:Me
0
THF/HOH,
* ; Lin,
Dieter, R.K.
CCBH17,
,H
c=c
’
Larock, R.C.
Y.J.;
54%
Dieter, J.W. (19841,
-J Org Chem,
$9, 3183
1 . Hg(OAc)2, T H F NaOAc, - 7 8 - 0°C n C 8 H 1 7CH=CHC02Me 2 . PdC12, LiCl MgO, MeOH, C O 80%
*
‘BO /B ‘0
24h
* : Narayanan,
-78OC K.
-
RT
(E : Z- = 9 8 : 2 )
J Org Chem, (19841, $9, 3411
SECTION 362
-
ESTER
415
OLEFIN
0
o v e r n i gh t t
L a r o c k , R.C.
c
; H a r r i s o n , L.W.; HSU, M.H. J Org Chem, (19841, ---
AcOH,
Pd(OAc)2,
L i O A> c
B g c k v a l l , J.-E.
d
*;
3, 3662
M e e o , ;
RT
\
7 6%
OAc
89%
( d l : m e s o = 6:4)
B y s t r i J m , S . E . ; Nordberg, R.E. J Org Chem, (1984), 3,4619 --C02Me
Mo ( C O ) * C P
M e 0 C/C'H
C02Me
Pearson, A . J .
/
* ; Khan,
C02tBu
C H =C
2
\
Me
CH2Br
Knochel, P . ; Normarit,
1 a. q K. O HTHF, , MeOH 20°C 2.
4 1 2 , MeCN,
M.N.I.
))I)) * J.F.
50°C
93 %
20°C
---J Am Chem
nBuCSCH, Z n THF,
Q$O
Soc, (1984),
*
C,
106,1872 02 t B u
CH =C
70%
\
CH2C=CH2 I nB u
Tetrahedron Lett, (19841,
25,
1475
416 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
N,
Cu(OTf)2, BnOH,
SECTION 362
reflux C02Bn
4h
63%
Smith 111, A.B.*; Toder, B.H. ; Branca, S.J. ---J Am Chem Soc, (19841,
106,3995
0 II L i O C C F 3 , CF3COOH 5% Pd(OAc)2,
RT
Ac OH
0qC 7F 5% 3
Backvall, J . - E .
Y
; Vagberg, J.: Nordberg, R.E. O
-
Tetrahedron L e t t , (1984),
0
25, 271 7
CH2=CHCH2SiMe3
n
a
o
0 -=RT
t
Me30 BF4
CH =C HC H C HC H =CH C H CH C 0 Me
-
94h
85%
* Fujisawa, T. : Kawashima, M.;
Ando, S. Tetrahedron E ,(19841,
25,
321 3
1 . C H 2 = C ( , 0 E t ) 2 , PhH cat.
P hCH =CHCH 2 0 H
(L)
PdC12(COD)
0°C
-
RT
P hCH=CHCH 2 C H 2 C 0 2 E t
2 . PdC12( PPh3)2 x y l ene, 4h
r e f 1 ux
Ohshima, M. ; Murakami, M. ; Mukaiyama, T. -Chem Lett, (19841, 1535
86%
SECTION 362
ESTER
-
41 7
OLEFIN
0 II P h C H = C H C H 20COMe
dPPe P d 2 ( d ba )
* *
CHCl 91 %
dioxane, reflux
Tsuji,
* J. ; Takahashi,
K.: Minami, I.; Shirnizu, I. Tetrahedron Lett, (19841,
-
25, 4783
0""'
1 . 37% H C H O , PhSH, RT c a t . TMG, 2 4 h
*
2 . A c 2 0 , Py 3 . n B u 3 S n H , AIBN 80°C, P h H TMG = t e t r a m e t h y l g u a n i d i n e * Ono, N. ; Kamimura, A.; Kaji, A. Tetrahedron Lett, (19841,
80%
25, 5319
-
0
II
Ph3P=CHC02Et, N E t 3
CH3CH2CC1 CH2C12,
Lang, R.W.; Hansen, H.-J.
RT, lh
t
Org Syn, (19841,
T H F , CH3CH0 25OC, o v e r n i g h t
PhCH=C
\
C02Me
2 . HOH
* S.E. : Hoole,
MeCH=C=C" 'C02Et
62,
64%
202
Me
1 . LiA1H4, CrC13 ,CH 2Br
,,\"'H
*
o?$ 0
83%
Drewes, R.F.A. Syn Catgun, (19851, 2,1067 Okuda, Y.: Nakatsukasa, S.; Oshima, K. : Nozaki, H. Chem Lett, (19851, 481 --
418 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
f 6
C02Me CH2=CHC02Me, d p p e P d 2 ( d b a )3 'CHC1 DMSO, 8OoC, 2 h T s u j i , J.
Shirnizu, I . ; Ohashi, Y.;
CHCl,, J
* ; Boden,
*
26,
3825 0 II
18h
reflux
E.P.:
C02Me
C02Me 84%
4
Tetrahedron Lett, (1985),
0 II Ph3P=CHCSEt,
*
0"'";' 91 %
(E:I =
Mabury, S.A. Chem, (19851,
-J Org
96:4)
50,
709
6 N i ( C 0 ) 4 , DMF
CI
2.2 IPrOH 70"C, Hirao,
4 Me02C
C02Me
Keck, G.E.
SECTION 362
* T. ; Nagata,
C02Me
6h
S.; Agawa, T.
Tetrahedron Lett, (19851,
1 L D A , THF-HMPA -78°C 2 . a q . NH4C1
Harris, F.L.;
CH2=CHCH2CH2C02nPr
* Weiler, L.
61 %
26,
5795
C02Me
60%
JCS Chem Conm, (19851, 1124 T e t s e s @, (1984), 25, 1333
SECTION 362
ESTER
t
-
41 9
OLEFIN
-
Ph3As-CHCH=CHC02Et Et20,
2OO0C,
4h
85%
NOz
*
Huang, Y. ; Shen, Y.; Zheng, J.; Zhang, S. Synthesis, ( 19851, 57 OTf
CH2=CHC02Me,
DMF
2% Pd(PPh3)2C12
t-BU
3 NEt3,
wuco
* t-Bu
75OC
91 %
Scoti, W.J.; Peia, M.R.: Swgrd, K.; Stoessel, S.J. ; Stille, J.K. --J Org Chem, (19851, 2,2302 1. AcOH,
120'C
C1 CH2COOH
nC8H1 7CH=CH2
Mn ( OAc )
2. NaI, 3 . NE't3,
.HOH
*op
a c e t o n e nC8H1, THF
(1
Fristad, W.E. * ; Peterson, J.R.; Ernst, A.B. --J Org Chem, (19851,
0 OSiEt3
C02Et
+
CH = C H P P h 3 B r KF,
MeCN
+
0
3
ICCgH17 2) 72%
2,31 43
-w
C02Et 18-crown-6 80% r e f 1 ux Marino, J.P. ; Laborde, E. J Am Chem Soc, (19851, 107, 734
*
420 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
,OTMS
1 . CHC12Ph,
MeCH=C
(E:Z
'OE
MeLi
2 . PhCH3, h e a t
t
= 85:15)
Ph
/
*
MeCH =C'\
(E:I
C02Et
il-
P(OiPr)3
Pd(OAc)2,
nBuLi,
THF,
4 0 p s i C02,
RT
THF
95%
4h
*
T r o s t , B.M. ; Angle, S.R.
OH I
(CH2)7
i
CHO
7 9%
79~21)
Tetrahedron, (1985) , 41, 2643, 2653
Slougui , N . ; Rousseau, G.
Me
SECTION 362
---J Am Chem Soc,
B
1 . (Et0)2PCH2C02Et K2C03, HOH 20°C
2 . KOH, a q . E t O H , 30°C 3 . H 3 0t
m
(19851,
PH
(CH2)5
I
CH=CHC02H 77%
V i l l i e r a s , J.*; Rambaud, M.; Graff, M. Tetrahedron Lett, (19851, MeCHO, EtO-C=CCH2SiMe3 -60
-
107, 6123
26,
TiC14
53
/ CH2SiMe3
CH3CH=C 0°C
Pornet, J.; Khouz, B.; Miginiac, L. Tetrahedron Lett, (19851,
\
C02Et
7 0%
26,
1861
SECTION 362
ESTER
421
OLEFIN
oso Ph
0
"B u S n H
,,,,+CEC P h
AIBN
0 C S e- P h nII
Bathe,
-
PhH,
2h
*
M.D. ; Bosch, E.
OC02Me
I
cC6H13 - r - C
CH
Tetrahedron Lett, (1986),
P d ( d ba ) q C H C 1
PPh3,
* Tsuji, J. ; Suguira, T.;
15h
*
CH3
/
9 0%
3, 641
C=C=CHC02Me
f i C 6 H 13
99%
Tetrahedron E,(19861,
3, 731
MgS04
*
xyl e n e , r e f 1 ux
" Y O SePh II 0
\
Minami, I.
DBU,
Carling, R.W.;
MeOH
5 atm C O , 4OoC
CH3
t
(5
* Holmes, A.B.
p c c 5 H 1 1 0
52%
JCS Chem Cam, (1986) , 325
1 . BrCH2CC2Me, N a 2 T e
DMF, T H F , -20°C
PhCHO
2 . a q . H2S04
*
Suzuki, H. ; Inouye, M.
t
Chem Lett, (19861, 403
PhCH=CHC02Me 73%
422 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
E, 0
0
0
,
I
SECTION 362
Mn02, AcOH
5% P d ( O A c ) 2 , 42h
RT 7 0%
Antonsson, T.: Hemann, A . : Moberg, C. JCS Chem cosla, (1486), 518
---
-4
C02Me
D M F , 4ii s i e v e TBAF
*
66%
Majetich, G. ; Desmond Jr., R.W.: Soria, J.J. -J Org Chem, (19861, 51, 1753 0
1 . PhCHO B F3 * O E t 2 2. Ht
OMe
Tanaka,
* K. ; Yoda,
Ph
80%
H.: Isobe, Y.; Kaji, A . J Org C k m , (19861, C H 2 = C H CH 2 C 1
H C E C CH C H C OOH
*
*
2,1856 '
k
5
THF, PdC12(MeCN)2 RT,
5h
J Am Cheat Soc, ----
0
94%
Yanagihara, N.; Lambert, C . ; I r i t a n i , K . ; Utimoto, K.
H.
0
(19861,
* : Nozaki,
108,2753
SECTION 362
ESTER
EtCOOH, PhCH3,
HCECfiB u
-
EtKo m-Bu
4h 5,
+
1% R U ( ~ ~ C O D ) ~
c o
*
0 EtAo
72%
0
Mitsudo, T. ; Hori, Y.; Yamakawa, Y.; Watanabe, Y. Tetrahedron Lett, (19861,
BrCH2C02Et, nPrCHO -
100°C,
nBu3Sb
+
2.5h
BnOCC=CHiPr 1 CH3
Piva, 0 . ;
hv,
CH2C12
(-)-ephedrine -78"c
2, 2125
=CHC02E t
9.~ 2%
Tetrahedron Lett, (1986),
II
2%
*
nPrCH
Huang, Y.; Shen, Y.; Chen, C. 0
Jr""
0
PBu3 80°C,
423
OLEFIN
3, 2903 0
1 I
*
B n O C CI H C H = C M e 2 CH 3
71 %
(28% ee R )
* Henin, F.; Muzart, J.;'Pete, J.-P.
-
Tetrahedron Lett, (1 986),
27,
3001
PdCl 2(PhCN)2 0
s.J,
t Ph
Auburn, P.R.; Whelan, J.;
10 min
* Bosnich, B.
Organometallics, (1986),
"Yo Ph 95%
2, 1533
424 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. Br2
0 II M e 2 C =CH CCH
Engler, T.A.
CH3
I
*
CH2=C-CH=CHC02Me
2 . N a O M e , MeOH
* ; Falter,
SECTION 362
(L:L =
97:3)
*
Ph
Tetrahedron Lett, (19861, 3, 4115
W.
6
1. PhCHO, CH2C12 /CH S n C B u
CH2=C
\
4 BF3*0Et2
-
-78°C 2 . CF3COOH,
C02Et
Baldwin, J . E .
*
RT CH2C12
Tetrahedron Lett, (19861, 27, 5423
c
PhSeC1, NEt3
*
CH2C1 2 , -78OC dark
CH20H
Taylor, R.J.K.
* ; Caton,
Daub, G.W.
0
9 5%
M.P.L.
Tetrahedron E ,(19861, 3, 5919
E t C (OMe)3 ____.___)
'CH3
"-d
SePh
\
PhCH=C/
77%
RT, overnight ; Adlington, R.M.: Sweeney, J . B .
, '( C H 2 ) 3 C O O H
Huckstep, M.R.:
66%
125OC
* ; Shanklin, .H +
Ph 16)
Ph
(84
Tata, C. J Org Chem, (19861, 51, 3402
P.L.:
-
-
8 0%
SECTION 363
ETHER
-
ETHER
425
1. LiN(TMS)2
2. M e 3 S i C 1 Me,Siy
3.
CH2N2
4.
KH
+
C H 3 C H = C H C H =CHCO,Me L
%to, T.; Tsunekawa, H . ; Kohama, H.: Fujisawa, T. Chem Lett, (19861, 1553 --
*
83%
Review: IISynthes i s of a-Me thylene- Y- Lac tones"
Sarma, J . C . ;
Sharma, R.P.
Heterocycles, (19861, 24, 441
Related Methods: Protection of Aldehydes (Section 60A) ; Protection of Ketones (Section 180A) Also via: Acetylenic e st e rs (Section 306) ; Olef i n i c acids (Section 322; 6-hydroxyesters (Section 327)
SECTION 363: Ether, Epoxide, Thicether Thioether
- Ether,
Epoxide,
See Section 60A (Protection of Aldehydes) ad Section 180A (Protection of Ketones f o r reactions involving formation of Acetals and Ketals.
54 1
PO(0S i M e 3 )
*
Hujama, T. ; Obayashi, M.
78%
Tetrahedron Lett, (19831, 24, 395
SECTION 363
426 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
6"
O\
CI C H 2 C H - C H 2 , RT
B u 4 N H S 0 4 , 3.5h
50% aq. NaOH
Mouzin, G.;
90%
Cousse, H.; Rieu, J.-P.; Duflos, A . Synthesis, (19831, 117 1 . THP-O(CH2)3CH0 2 . camphor-S03H
o P P II h 2
MeOH
0 Ley, S.V.
* : Lygo,
B.
-
Tetrahedron Lett, (1984), 25, 113
H S i Et 2 M e 25"C, PhH, 3 h Murai, T.; Kato, N.
58%
0 s iE t 2 M e
(4
t
'+ " C H 2 0 S i E t 2 M e
* S.; Murai, S. ; Toki, T.; ---J Am Chem
Soc,
88% SuzuKi, S.; Sonoda,
(19841, 106,6093
1 . LBuLi, pentane/THF -78°C 2 . I(CH2)30SiMe2tBu T H F , -10 3. aq. H F
Amouroux, R.
?+
-
50°C
Heterocycles, ( 1 9841, 2, 1489
66%
SECTION 364
ETHER
-
HALIDE
SECTION 364: Ether, Epoxide, Thioether OH
- Halide, Sulfonate
1 . NaBr, 18-crown-6
RT, 5 min
CH2C12,
,,
2 . mcpba, 0°C 5 min Mechoulam, R.
Srebnik, M.:
427
*
80%
CH3CN,
0°C
*
&,
A ,
6
Melany, M.L.; Winstead, Thompson, Bunnelle, Thompson,
80%
J.; Harigaya, Y .
Tetrahedron Lett, (19841, --
1 . T i C H1 42 C, 1 - 4 5 ° C 2. MeOH, 3N HC1
Lock, G.A.;
\#”
H
0 Ts
* : Grote,
ooTs
b.
HO
12, NaHC03
Williams, D.R.
(19841, 1070
JCS Chem Cam, ---
CI %
25, 5231
f&
(97% ee)
9 5%
Thompson, D.W. Chem, (1985), 50, 3925 R.C.4 Simpson, T.H.; Lock, G.A.: Schiavelli, M.D.: D W J Org Chem, (19861, 51, 275 * Seamon, --W.H.,; D.W.; Mohler, D.L.; Ball, T.F.: D W. Tetrahedron Lett, (19841, 25, 2653
..
.
--J Org
428
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CH30CH2COOH
Stadlwieser, J.
*
1. S0Cl2,
12OOC
2. A1C13,
80°C
\
CH30CH2C1
7 8%
Synthesis, (1985) , 490
,
Pb( OAc)4
\
w
SECTION 364
D M E , O"C,
ZnBr2
10 min
*
86%
*
Motohashi, S. ; Satomi, M.; Fujimoto, Y. : Tatsuno, T. Heterocycles, (1985), 23, 2035
THF,
*
*
Posner, C.H. ; Haines, S.R.
20 min
Tetrahedron E ,( 1 985) , 26, 5
12, N a H C 0 3 , Et20/HOH,
0°C
2h '
(I:E
Tamaru, Y.;
* Kawamura, S.; Yoshida, Z.
&.
b = 98:2)
-
Tetrahedron Lett, ( 1 985),
I
26, 2885
98%
SECTION 365
Purrington,
Review:
-
ETHER
* S.T. ; Correa,
429
KETONE
57% (19861, 51, 1080
2 9 e,
I.D.
"Organic Synthesis with a-Chlorosulf ides"
Dilworth, B.M.:
McKervey, M.A.
Tetrahedron, (19861,
0
SEZTION 365: Ether, Epoxide, Thioether
Carless, H . A . J .
-
92,
3731
Ketone
69%
* ; Fekarurhobo,
G.K.
-
Tetrahedron Lett, ( 1 9 8 9 , 2$, 107
1. Ni(R)
Ph
2. H30
Curran, D.P.
* ; Singleton, 1 . LDA,
t
42%
D.H. Tetrahedron E,(1983) , 2, 2079
THF,
-8O'C
SCPr
2. To1 S02-SCPr -8O"C,
Scholz, D.
*
16h
83%
Liebigs Ann Chem, (19831, 259, 264 e s h Chem, (19831, 2,655 7
430 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0
0 SiMe,
Sakurai,
PhCH(OMe)2,
CH2C1
SECTION 365
g
~
i
h
1 0 % M e 3 S i I , -35OC
* H. ; Sasaki,
87%
(erythro:threo
K.; Hosmi, A. --Bull Chem Soc
CoMe
e, (19831,
= 99:l)
56,
3195
OMe
TMSOY
PhCHO
Eu(fod)3,
Danishefsky,
CHC13
*
0
Ph 85%
* S. : Harvey, D.F.; Quallich, G.; Uang, B.J. -J Org C h m , (19841, 3, 392
0
I1
PhCH =CHC P h
(L)
0 c a t . H ( N H C H ItC ) l ONHBu hPr / -+ . . , " Ph
*
NaOH, H 2 0 2 , CC14 2-methyl butane,
Banfi, S.; Colonna,
H
76%
RT
(95% ee)
* S. ; Molinari,
*
H.; Julia, S. : Guixer, J. Tetrahedron, (19841, 110, 5207 1 . C O ~ ( C O ) ~R ,T
CH3C5CCH20CH2CH=CH2
2.
6ooc
24h
Billington, D.C.
* ; Willison,
D. Tetrahedron
* I
3 6%
E, (19841, 25, 4041
SECTION 365
-
ETHER
0 II CH2=CHCCH3,
6h
K-10 c l a y , Fe
*
Laszlo, P. ; L u c c h e t t i , J.
+3
65% (exo:endo = 0 . 6 : l )
Tetrahedron Lett, (1984),
Sn(OTf)2, -78
-
3, 4387
fiP
8
PhSCH2C02Me, C H 2 C 1 0°C
A
7 5%
N%N-TMS Shimizu, M.;
431
KETONE
Akiyama, T.; Mukaiyama, T.
Chem Lett, --
(1984), 1531
1 . ( C O C1l .)5, ,h P h H 2. NEt3, COOH S n i d e r , B.B.*(' S n i d e r , B.B.*f
M 'e t
PhH
r e f l u x , 2.5h
Me
66% a # e 7 % %Me
-
JOrg Chm, (1985), 50, 5167 Hui, R.A.H.F. Hui, R.A.H.F.; Kclkami, Y.S. 3 Am Chem Soc, (1985), 107, 2194 ---1 . (COCl)*, PhH R T , 3h r e f l u x , 6h
Brady, W.T.
* ; Giang,
Y.F.
J Org chepa, (19851,
60%
50,
5177
432 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0
It
CH 2 O
CH3CCH3
nC5H1 S - N a Sabirov, S.S.:
SECTION 365
n C 5 H 1 1SCH2CH2CCH3 -
t
61 %
Gnevasheva, L.M.; Ismailov, M . I . ; Isobaev, M.D. J Org Chem USSR, (19841, 20, 1239 1 . KH,
THF,
-
-11 2. gl
.
HMPA
25OC
AcOH,
HOH
SPh
*
Cohen, T. ; Yu, L.-C.; Daniewski, W.M. J Org Chem, (1985), 1 . SnC12.2H20,
EtOH,
2.
ice
3.
pH 8
4.
l e v u l i n i c acid, 0.1N H C 1 ,
Varma, R.S.: Kabalka, G.W.
@@/Yh
*
'Ph
80°C 7 9%
>
2,443
(y;.
S ~ Conrmrn, I (1985),
c1 04-
4596
RT
3.5h
PhCH(OMe)2, CH2C12 -78OC
Mukaiyama, T.; Iwakiri, H.
50,
69%
86%
(=n:anti
= 88:12)
Chem L e t t , (19851, 1363
-
ETHER
SECTION 365
433
KETONE
PhCHO,
Me2AlCl
CH2C12,
-78OC
88%
*
Naruse, Y.: Ukai, J.: Ikeda, N.: Yamamoto, H. Chem Lett, (19851, 1451
--
1 . CH2=C,
,OSiMe
tBu 2-
/
0
II
*
T r C 1 0 4 ,P h C H 2 C 1 2 -78OC, l h
Me2C =CCH
2 . PhCHO,
OSi f P
h
y
-78OC
3. aq. NaHC03
MeCH=C,
S,
Ph Me
M e O H /CH,Cl,, L
Takeda, T.
91 %
Chem Lett, (19861, 221
Kobayashi, S . : Mukaiyama, T.
3t
,
TiC14
> L
-23°C
1 .5h
; Kaneko, Y.; Fujiwara, T.
0
II
Me2CHCCH2N02 HMPT,
Miyake,
87%
-
Tetrahedron Lett, ( 1 9861,
PhSH, A I B N
* H. ; Yamamura,
h
90°C,
3, 3029 0
>
I1
Me2CHCCH2SPh
2h
69%
K.
Bull Chem Soc Jpn, (19861,
2,89
434 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1.
(Me0)2CHCH2CH2SnMe3 TMSOTf
*
2 . TiC14
$Me
3 . PDC
Lee, T.V.
SECTION 365
* : Richardson,
Taylor, D.A. Tetrahedron E ,(1986),
K.A.;
83%
3,5021
CH2C1
Pirrung,
* M.C. ; Werner,
2 Am
J.A.
9 5%
Chem
SOC,
(19861,
Ph
6h
57% Roskamp, E . J . ;
Johnson, C.R. 1.
OH21 OH
?4
---J Am Chem
17%
Soc, (19861,
108,6062 0
dioxane
5% Bu4NHS04,
6OoC
>
I1 E C 1 0H 2 1 O C H 2 C C H 3
2 . 1 % a q . H2S04, 60°C 71 %
dioxane
Gu, X.-P.:
bMe
( C 1 CH2)2CHOCH20Me NaOH, a q .
"1
108,6060
Ikeda, I . ; Kornada, S.; Masuyama, A , ; Okahara, M.
--J Org Chem,
(1986),
2,5425
*
SECTION 366
-
ETHER
NITRILE
SECTION 366: Ether, Epoxide, Thioether
-
435
Nitrile
Me3S i C N h
TiCl
HO'Me (95
CH2C1
Elliott, J.D.
* : Choi,
V.M.F.;
PhCH2CN
Makosza, M.
Bu4NBr, t
98%
5)
Johnson, W.S.
--J Org Chern,
iPrCHO,
HO
(19831, 48, 2294 0
50% NaOH 2OoC,
l h
/ \
t
Ph-C-CHiPr
1
; Kwast, A.; K w a s t , E.; Jonczyk, A.
-J Org C h m , TMS-CN,
( 1 9851,
Zn12
CH3CH(OMe)2 25OC,
CN
2,3722 CN
I
w
CH3CH OMe
15 min
63%
Kirchmeyer, S.; Mertens, A.: Arvanaghi, M . ; Olah, G.A. Synthesis, ( 19 8 3 , 498
0
M e 0 OMe
*
1 . LBuNrC, CH2C12,
-78
2. a q . NaHC03
-
O°C
*
CN
-0 Me0
TiC14
80%
*
I t o , Y. ; Imai, H.; Segoe, K.; SaeguSa, T. -Chem Lett, (19841, 937
92%
436 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
2 NaBH3CN,
cat.
20 tBuN=C,
tBuOH
,
r e f 1ux
nBu3SnC1
Stork,
BoEt
AIBN
t
“’CN
4h
* G. ; Sher,
60%
J Am Chem ----
P.M.
SECTION 367
(19861, 108, 303 (19831, 6765
105,
Soc, J Am Chem Soc,
----
SECTION 367: Ether, Epoxide, Thioether
-
Olefin
En01 ethers are found in this section. 0 II Ph2PCH(OEt)2
CH=C
>
(OE t ) 68%
van Schaik, T.A.M.;
8
-
2.2
nBuSCHCH2CH3
I
CH3
Miller,
HN(TMS)2,
2 TMS-I,
* R.D. ; McKean,
&
*
Henzen, A.V.; van der Gen, A. Tetrahedron Lett, (19831, 24, 1303
14h, 25°C
D.R. -
CH2C12
* EtCH=CHSCHCH2CH3
d5
(L:L=
67:33)
-
Tetrahedmn Lett, (19831, t
CH2=CHCH-AsPh3 THF,
-
*
-78’C-RT
Ousset, J.B.; Mioskowski, C.*; Solladie, G. Tetrahedron Lett, (19831,
-
81%
211, 2619
65%
2, 4419
SECTION 367
ETHER
PhCH3,
-
437
OLEFIN
7OoC, 6h
84%
Hartner Jr., F.W.: Schwartz, J.; Clift, S.M. J Am Chem Soc, (1983), ----
105, 640
,Si E t
0.1 Pd(PPh3l4
RT
CCl,,
95%
Stanton, S . A. ; Felrnan, S.W.; Parkhurst, C.S.; Codleski, S.A. J Am Chem Soc, (19831, 105, 1964 ----
*
OMe
0 II
PhCR'
. ,
Me?
CDC13, 4 8 h
0 . 5 '% E u ( f o d ) 3 R = OTMS, R '
* f4i R%0
= H
Bednarski, M.: Danishefsky, S.* ---J Am Chem Soc, (1983), R = H,
R ' = Me
1 0 KBar, 20h
Jurczak, J.; Colebiowski, A.; Bauer, T. /
OEt
(C0)4Fe=C
\
Ph
Ph
Semlhack, M.F.*:
82%
105, 3716
81%
(E:I =
1:l)
Synthesis, (19851, 928 Ph
CH2=CHPh,
5OoC
55 p s i COY l h
Tamura, R.
2
>
I
EtOCHCH=CHP h
60% Am Chem Soc, (1983),
(El
3, 6750
438 CCNPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
O, M CH2=C=C
\
e
PhZnC1,
Ph
THF
2% P d ( P P h 3 ) 4
CMe2
I
SECTION 367
I
*
C H 2 = C - CI= C M e 2 OMe 9 5%
OAc
Kleijn, H.; Westmijze, H.; Meijer, J.; Vermeer, P. Rec Trav Chim Pays Bas, (19831, 102, 378 ---
Me
BF3*OEt2,
0
Et,
1\
/
C-CHSiMe2Ph
c
5 min
CH2C12,
* Fleming, I. ; Newton, T.W.
-78OC
t
Me
,C = C H O S i M e 2 P h /
68%
(-E :-Z
= 4:96)
JCS Perkin I, (19841, 119
tBu
-1
L iN-toc t y l
TMS-C1,
+ .
-78°C THF
Corey, E.J. * ; Gross, A.W.
(97.5
2.5)
:
-a
Tetrahedron=,
(19841,
25, 495
OSi!leEt2
HSiEt2Me,
PPh3
co2(co)8,
12OOC
50 a t m CO
0 s iM e E t
88%
*
Chatani, N.; Furukawa, H.; Kato, T.; Murai, S. ; Sonoda, N. J Am Chem Soc, (19841, 106,430 ----
SECTION 367
ETHER
-
4 39
OLEFIN
1 . H g ( O A c ) 2 , g l . AcOH
nu
RT, 30 m i n
CsCnPr 2 . NaBH4, NaOH 63%
*
---J Am Chem
Larock, R.C. ; Harrison, L.W.
Soc, (19841,
1 . i B u M g B r , E t 2 0 , 6h C p 2 T i C 1 2 , 0 - 25'C
T M S - C E C C H 0H
2 ' fic6H13hcH3 0 3 . B F 3 * 0 E t 2 , CH2C12
*
Sato, F. ; Kanbara, H.: Tanaka, Y.
90%
Tetrahedron Lett, (1984) ,
1 . 3 L D A , T H F , -1OOC
0 II P hSnB u
2 . TMS-C1,
-1 0
*
Miller, R.O. ; Hiissig, R.
-
-
25°C
25, 5063 PhS
b
\
/C=CHEt 8 0% (E:L = 2 : l ) Tetrahedron El(1984), 25, 5351
3 . a q . NaHC03
t
106,4218
TMS
1. nBuLi, THF HMPA 2. gCgHl9CHO 80%
*
Ousset, J.B.; Mioskowski, C. ; Yang, Y.-L.; Falck, J.R.
*
Tetrahedron Lett , ( 1 984) , 25, 5903
8"'
440 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
6
1 . LiCHPh(OMe), 2.
RT
CS2,
3. MeI,
-
THF,
reflux
reflux
*
4 . nBu3SnH, AIBN reflux,
Vatele, J.-M.
*
n
-78°C
PhH
-
Tetrahedron Lett, (19841,
SECTION 367
62%
(I:r = 4:6) 25, 5997
pTsOH * H O H PhH,
18h
~
r e f 1ux (Dean S t a r k )
*
Nickon, A. ; Rodriguez, A.D.;
do
-
e
,
S h i r h a t t i , V.;
,
(1985),
cat.
*
nBu3SnOPh, THF
CH3CH=CHCHnPr
Keinan,
* E. ; Sahai,
Pd( PPh3)4, M.;
RT
82%
87%
(111)
T o r i i , S. ; Inokuchi, T . ; Yukawa, T. --J Org Chem, (1985),
I
4218
NaOH
= chloropyridine cobaloxime
OA c
Ganguly, R.
50,
E t 4 N O T s , MeOH
L - E t
cat.
60°C,
67%
50,
5875 OPh I
>
CH3CH=CHCHnPr Ph
p
t
C H CH C H = CHcPr
*
Roth, Z.; Nudelman, A. ; Herzig, J. J Org Chem, (1985), 50, 3558
S E C T I O N 367
-
ETHER
OLEFIN
441
0
0 SiMe, (CO)5MnSiMe3, RT,
CD3CN
3h
88%
Marsi, M.; Brinkman, K.C.; Gladysz, J . A .
Lisensky, C . A . ;
--J Org
Vaughn, G.D.;
50, 3396
Chem, (19851,
OM e
2C5H11, Me
/
c =c
/
C H =C HC<
/H
\
*lMe2
*
Pd(PPh3)4
Chatterjee, S.; Negishi, E.
*
(E:l = --J Org Chem,
Me2S-SMe B F 4 - ,
I
f i C 5 H 1 l-;-SMe
CH2C1
*
CH2=CHCH2SnBu3
CH3
-23OC,
Sato, T.
,c=c
Me
t
SMe
Trost, B.M.*;
OMe
2c5H11,
\
H C H 2 C H =CHOMe
69%
2:l)
(19851, 50, 3406 SMe
I nC5H11CCH2CH=CH2 -
I
l h
_--J Am Chem Soc,
/
CH3
(19851,
107, 779
89%
1 . Me3N-0.2H20
O s 0 4 , LBuOH reflux,
nC 6H,
24h
CH =CH S iM e 3
(I)
Hudrlik,
* P.F. ;
t
2.
20% a q . NaHS03
3. 4.
Et20
NaH, HOH Hudrlik, A.M.:
"C6H1
3CH=CHOSiMe3
(I)
Kulkarni, A.K. (1985) , 107, 4260
J Am Chem Soc, ----
51 %
442 COMPENDIW OF ORGANIC SYNTHETIC METHODS VOL 6
E t 2 0 , 0°C
PhMgBr,
*
CH2=CHCH(OEt)2 NiC12(dppp),
Sugimura, H.; Takei, H.
BrCH2C02Et
3h
Chem Lett, (19851, 351
n B u 3 S n S n n B u 3 , TMS-C1 80°C
Pd(PPh3l4,
t
60% 97:3)
CH2=C
t e t r a 1 in, 20h
*
EtOCH=CHCH2Ph
(1:I=
*
SECTION 367
Kosugi, M. ; Koshiba, M.: Sano, H.; Migita, T.
/Et
\
O S i M e ,3
69%
*
E?ull Chem Soc Jpll, (1985), 58, ---
nBu3SnCH2CH=CMe2, THF
d
*
50°C
n B u C E C C H S i Me -
1%
CH2=C=C
(-PdC1/2
/
\
1075
nB u -
C\HOEt iBu
Pornet, J. ; Miginiac, L.*;'Jaworski, K. ; Rondrianielina, B. Organcnnetallics, (19851, 4, 333
Ph3Sn(CO)3Co=C
/OMe \
Ph
2.5 EtCSCEt PhH,
Ph
50°C
6h
* Wulff, W.D. ; Gilbertson, S.R.;
Springer, J.P.
J Am Chem Soc, ----
(1986),
93%
108,520
7 6%
-
ETHER
SECTION 367
OLEFIN
Pd ( P P h 3 )
""0 c s M e
Me\+"
CHC13,
II
Me'+,,
25°C
O<# "' S H
95%
l h
S
Auburn, P.R.:
*
443
Whelan, J.; Bosnich, B. JCS Chem Comn, (19861, 146 ---
71 %
Overman,
* L. E. ; Castazeda, A. ; Blumenkopf f , T. A. J Am Chem Soc, (1986), 108,1303 ---1 . fiBuLi, 2.
BnCN
THF,
-85OC
[PhSMe/NCS/CC14],
3 . fiBuLi,
-85
-
THF
*
-30°C
P hSCH=CH P h
4 . HOH
52% Harada, T. ; Karasawa, A. ; Oku, A.
* --J Org Chem, OMe
tB~cH(0Me)~ MeCH=CHCH2S i M e 3
(L) Hosomi, A.
_____)
t-Bu+-
Me
TiCl
* ; Ando,
CH2C12, 6 h - 7 8 - 0°C
M. ; Sakurai, H.
(96
*
51,
(19861,
+ B-tu*
OMe Me
4) 63%
Chem Lett, (1986) , 365
842
444 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
nC7H1 5CH(OMe)2
CH2=CHCH2SiMe3
f
nC7H1
SECTION 367
OMe
I
5CHCH2CH=CH2
K10 c l a y , O°C C H 2 C 1 2 , 30 m i n * Kawai, M.; Onka, M. ; Izumi, Y. Chem Lett, (19861,
II
MeSCH 2C Ph
JCS Chem Canm, (19861, 531
v/, CH2C1
2 8 O C , 4h
*
381
a52
Aguero, A,; Kress, J.; Osbofn, J.A. 0
90%
hv
* ~
cJ*o 7 0%
21 %
Vedejs, E. ; Eberlein, T.H.: Mazur, D.J.: McClure, C.K.; Perry, D.A.; Ruggeri, R.; Schwartz, E.; Stults, J.S.; Varie, D.L.; Wilde, R.C.; Wittenberger, S. J Org Chem, (1986), 51, 1556
cat.
= chloro(pyridin0)-Q-(dimethylglyoximato)
c o b a l t (111)
*
Bhandal, H.: Pattenden, G. ; Russell, J.J. Tetrahedron Lett, (19861,
3, 2299
SECTION 367
-
ETHER
*
Boudjouk, P. ; So, J . H .
PhCH=CHCH2SiMe3
Syn Canmrn, (19861,
e
445
OLEFIN
16,775
OMe I
P hCHCH =CH
MeOH
(63)
+
C electrodes MeCN E ~ ~ N O T S PhCH=CHCH20Me ( 3 7 ) Yoshida, J . ; Murata, T.; h o e , S.
*
fi
-
Tetrahedron Lett, (19861,
0
r O ! O M e
T r o s t , B.M.
*
EtSSiMe3 3% dppe, 1 % Pd ( d b a )
rVMe 9 5%
r e f 1 ux
T M S - C H 2 f = C H 2, 2 5 % PPh 3 CH20Ac ; King, S.A. Tetrahedron=,
89%
(19861, 3, 5971
Review: f l S i l y l Enol Ethers I n SynthesisT1 Brownbridge, P.
3, 4141
THF
20% IBu3SnOAc
PhCH =CHCHO
Tro st , B.M.
*CHC1
3, 3373
RT, 9 6 h ; Scanlan, T.S. Tetrahedron Lett, (19861, 5% P d ( O A c ) 2 ,
*
THF
7 6%
Synthesis, (19831, 1 , 85
Related Methods: Prot e c ti on of Ketones (Section 180A)
446 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 368: Halide, Sulfonate
-
SECTION 368
Halide, Sulfonate
Halocyclopropanations a r e found i n Section 74F ( A l k y l s from Olefins).
oo
Croft, A.P.:
PPh3,
CC14
reflux,
2d
Bartsch, R.A.
*
P
J Org Chem, (19831,
s,3353
74%
70% * Arzoumanian, H. ; Krentzien, H.: Lai, R.; Metzger, J.: Petrignoni, J.-F. J Organomet Chem, (19831, 3, 175
-
17% PhI(OH)OTs, Me2C=CH
OTs I Me2iCH20Ts
0°C
t
CH2C12, 3 6 h
54%
Rebrovic, L.:
P r CH=CHnPr
rtl I
_
J Org Chem, (19841,
Koser, G.F.
Mn(OAc)3,
0 II
c1
I
CH3CC1
EPrCHCHcPr I
\
Donnelly, K.D.; Selle, B.J.
AcOH ,
O O C ,
Fristad, w.E.";
s,2462 I
5h
(-r n e s o : f l = 1 1 : l ) c 1 7 1 % k l l e r m a n , B. J . : Peterson, J.R. :
Tetrahedron Lett, (19841,
-
25, 607
SECTION 368
HALIDE
-
447
HALIDE
1 . P h S e C l , MeCN
cC5H1 C H = C H C H 3 (I)
2. C12,
CC14
ref1 ux, Bu4NC1 3 . H202
Morella, A.M. ; Ward, A.D.
*
c1
1
w
nC5H1 CHCHCH3 -
I
c1 (erythro)
Tetrahedron
87%
E ,(19841, 3,1197
1 . TeC14, C C 1 4 2 . LBuOOH, dioxane
r e f l u x , 30 min
Uemura,
* S. ; Fukuzawa,
S.
t
-J Organmt Chem,
90%
(19841, 268, 223
Me2NBr, B F 3 . 0 E t 2 CH2C12,
RT
w
66% Heasley, J.M.; Stark, S.R.; Robinson, B.L.: Heasley, V.L.; Shellhamer, D.F. Tetrahedron Lett, (1985), 26, 181 1
* G.E. ; Janes,
*
Napolitano, E. ; Fiaschi, R.; Mastorilli, E. Synthesis, (19861, 122
77%
448 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
* Barluenga, J. ; Martinez-Gallo, J.M.; J Chem Res, ---
SECTION 369: Halide, Sulfonate Ph,
Ac 0'
/
c =c,
H
Me
-
7 5%
Najera, C.; Yus, M. (1986), 274
Ketone
P t electrodes
e-,
SECTION 369
3 HF, NEt3
0
*
!I
PhCCH CH3
1
F
Laurent, E.; Tardivel, R.; Thiebault, H.
Tetrahedron E,(19831,
24, 903
63%
NaBr202, a q . A c O H
RT, 5 h Kageyama, T.
* : Tobito, Y.;
*
87%
Katoh, A . ; Ueno, Y. ; Okawara, M. Chem Lett, (19831, 1481
7-
86%
Arrieta, A . ; Ganba, I.; Palomo, C.
S 2 Coarmrn, (19841,
2,939
SECTION 369
-
HALIDE
* Olah, G.A. ; Ohannesian, L.;
KETONE
4 49
86%
Arvanaghi, M.; Prakash, G.K.S. Chem, (19841, 2,2032
--J Org
m:
0
-N
I1
PhCCH3
C12,
0
CH2C12,
t PhCCH21
RT
*
+
II
PhCCH2C1
(1
18h
3ket, B.; Zupan, M.
0
II
Me(IC14)-
Tetrahedron, (1984),
18.4)
110,
97%
2865
0
I\
nC5H1 CCH3
0
tBuBr,
ii
DMSO
650°C,
6h
t
*
n C 4 H 91C H C C H 3 Br
A r m a n i , E.; Dossena, A.; Marchelli, R. : Casnati, G. Tetrahedron, (1984), 40, 2035 0 I1
C13CCC1, Et20,
* Mehta, G. ; Rao, H.S.P.
88%
Zn(dust) l h
Syn
CI CI CbEfnRI,
(1985),
3, 991
80%
SECTION 369
450 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
[LDA,
1.
CH2Br2],
-9OOC
0
2 . EBuLi PhCH2CH2C02Et 3. CH3iCl
6
,
EtOH
*
1 . LDA,
II
PhCCH3
Rozen,
75%
J Org Chem, (19851,
THF,
-78°C
-
2 . CH CF, -78OC 3 11 0 3 . Na2S203
S.
* ; Brand, M.
PhCH 2 C H 2 C C H 2 B r
-78°C
Kowalski, C.J. ; Haque, M.S. 0
i1
t
RT
*
50,
5140
0
II
PhCCH2F 75%
Synthesis, (1985), 665 0
BF3.0Et2,
RT,
*
90 m i n
87%
Syn Cornnun, (1985),
Hiegel, G.A. ; Peyton, K.B.
3, 385
hBrf - -
0
Ii
O
0
N
H
PhCH=CHCCH3 Et20,
RT,
t
ii
PhCH=CHCCH2Sr
10h
80%
Grundke, G.; Keese, W.;
* Rimpler, M. Chem Ber, (19851, 9, 4288 --
SECTION 369
HALIDE
Castaldi, G .
*
-
KETONE
451
94%
Br
( S : ! * = 93:7) ; Cavicchioli, S.; Giordano, C. : Uggeri, F. Angeu Chem Int ----
Ph, Me2 C =CHCH 2 0 H
TMSO’
Ed
x, (19861, 25, 259
CH3N02,
* BF3*0Et2
II
ti
PhCCHCH2CH2CCH
30 m i n
O O C ,
0
0
C=CHC1
I
ci 60%
Poirier, J.-M.; Hennequin, L.; Fomani, M. Bull Chem Soc F’r, (19861, I1436
----
87%
( a l s o f o r 0 , f l~u o r i n a t i o n o f p h e n o l s )
*
Umemoto, T. ; Kawada, K.; Tomita, K. Tetrahedron Lett, (19861,
3,4465
1 . BH3-Me2S
0
nC 5 H 1 CECTMS Page, P.C.B.
36
2 . M e 3- N - 0
t
Br
3 . NBS
; Rosenthal, S.
ll
nC5H1, f H C S i M e 3
-
Tetrahedron Lett, (19861,
61 %
3,5421
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
452
1 . TMS-Br,
DMSO
MeCN, 1 . 5 h RT
*
o". dBr Br 0
a 5%
2 . HOH
12%
Bellesia, F.; Ghelfi, F . ; Grandi, R . ; Pagnoni, U.M. J Chem Res, (19861, 428 ---
Review: Ifa-Fluoro Carbonyl Compounds" Tetrahedron, (19851,
Rozen, S.; F i l l e r , R.
SECTION 370: Halide, Sulfonate
0
II
CH3CHCNH2
I
c1 Kaiser, D . A . ;
0 It PhCCH3
-
*
2, 1111
Nitrile
P205 on ' S i c a p o n t ' DMF, r e f l u x , l h Kaye, P.T.
SECTION 370
c1
I
*
CH3CHCN 60%
Syn c<mmun, (19841, 14, 883
1 . TMS-CN,
3 TiC14,
CH2C12,
0°C - RT
2 . HOH
Id
*
Kiyooka, S. * ; Fujiyama, R . ; Kawaguchi, K . Chem Lett, (19841, 1979
--
c1 I Ph-C-CH3
I
CN 65%
SECTION 371: Halide, Sulfonate
nC8H1 7CsCH Kabalka, G.W.
OLEFIN
*:
453
- Olefin
b
2 . HOH
BrCH=CHnC8H1
I-=, ZI
3 . NCS, a q . N a B r , T H F 63% S a s t r y , K.A.R.; Knapp, F.F.; S r i v a s t a v a , P.C. Syn Camnrn, (19831, 13,1027
--
HMPT, Br(CH2)5Br
-
195
* ; Landgrebe,
Kraus, G.A.
-
HALIDE
SECTION 371
5 min
b
220°C
B r ( CH2 ) 3CH =CH
Synthesis, (1984), 885
K.
NaOH,
57%
12,
81% B( O i Prl2
2 . N a O M e , MeOH
* : Samayaji,
Brown, H.C. c1
-25°C
V.
-
RT
Synthesis, (19841, 919 OMe
PhCH (OMe) 2 , 1 Oh
I
Me3S iCHCH=CH2
B F 3 * O E t 2 , CH2C12 0°C
*
Hosmi, A. ; Ando, M.;
80%
-
RT
Sakurai, H.
*
*
I
PhCHCH2CH=CHC1
(I:E
= 85:l 5)
85%
Chem Lett, (1984), 1385
454 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
“‘gH13,
-E - C 1 CH=CHCl
H
+ -
c=c, H’
SECTION 371
iBu2
2OoC,
6h
3CH=CHCH=CHC1
!C6H,
(EYE)
Ni ( P P h 3 l 4 PhH/ h e x a n e
80%
Ratovelmanana, V . ; Linstrumelle, G. Tetrahedron E ,(19841, 1 . nBuLi/CuBr-SMe2, -25°C
HCSH
2.
-
1 2 , THF, - 6 0
25, 6001
THF
-1OOC
t
nBuCH=CH I
(I)
3 . NaHS03
Alexakis, A . ; Cahiez, G.;
cat,
* J.F.
Nomat, O r g z , (19841,
C u C 1 2 , MeCN,
Hegedus, 0 II
62,
1
CH2C1
PdC12(MeCN)2
PhCH=C=CH2
* L.S. ; Kambe,
7 5%
O°C
(EE:ZZ --
3d N.;
I
t
= 2.8:l)
I s h i i , Y . ; M r i , A.
-J Org Chem,
1 . c p ; )@
-
P hCH=C f =CH P h c1
(19851,
50,
52%
2240
1 ”
CH2C12, 2.
Hudrlik,
KOH,
-78°C
EtOH
* P.F. ; Kulkarni,
-
RT
t
V
‘
46% A.K.
Tetrahedron, (19851,
3, 1179
SECTION 371
HALIDE
1 . C12,
20°C
2 . a q . Na2S03
Kunda, S.A.; Smith, T.L.;
455
OLEFIN
CH2C12
-
( O H ) ~ B C H = C H ~ ~ C ~ H 0~
-
reflux,
C1 CH=CHnC8H1
t
(z)
3h
81%
Hylarides, M.D.; Kabalka, G.W.* Tetrahedron E,(1985) , 26, 279
1 . B B r 3 , CH2C12 -78°C
nC 6 H 1 3 C 3 C H
-
RT
nCgH 1 3,
2 . TolS02N(C1 )Na.xH20 NaBr,
NaOAc,
Br
0°C
a q . THF Hara, S.; Kato, T.; Shimizu, H.; Suzuki, A.
-
#
Tetrahedtm Lett, (1985),
t
/
C=CHBr
84%
2, 1065
1 . MeMgBr 2. pF6
3 . ArMgBr
4. Ar
z
Ph3CtPF6-
1 2 , MeCN *Me'
-
j O O M e
Pearson, A.J.
nC8H1 7MgC1
#
: Khan,
1)
(2
20°C
Md.N.1. Tetrahedron Lett, (1 9851,
-
5 C1CH=CC12, 2 0 ° C 5% Pd(PPh3)4,
E t 2 0 / P hH
6h
72%
26,
1407
nC8H1 7CH=CC1
* J.-F.
Ratovelomanana, V.; Linstrumelle, G.; Nonnant, Tetrahedron E ,(19851,
65%
2, 2575
456 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . NaI, B F 3 . 0 E t 2 M e C N , 0°C
OH
1
CH2=CHCH ( C H 2 ) 4 0 H
* Vankar,.Y.D. ; Rao,
Tomioka,
I i CH2=CHCH(CH2)40H
a q . Na2S203
Tetrahedron Lett, (1985),
-
C.T.
* H. ; Hayashi,
(E:L =
-
Cy,
NEt3,
26, 1651
60h
* A. ; Martinez
* ; Chen,
26, 2717
120°C
86%
Alvarez, R.; Garcia Fraile, A.
Synthesis, (1986), 222
(E:Z Curran, D.P.
71I
94:6)
Inoue, N.: Izawa, Y. Tetrahedron Lett, (1985),
N.;
Mg12,
Garcia Martinez,
*
2 . O"C,
SECTION 371
M.-H.;
K i m , D.
J Am Chem Soc, ----
= 3.3:l)
-
(19861, 108, 2489
HALIDE
SECTION 371
-
OLEFIN
457
4 C r C 1 2 , DMF/HOH pH 3 . 5 ,
Wolf, R. ; Steckhan,
0°C
16h
* E.
88%
JCS Perkin I, ( 1 9861, 733
1. nPrBHBr.SMe2,
0°C
Et20 2.
-nC6H1 3 C 3 B r
NaOMe,
MeOH,
3 . B r 2 , CH2C12, 4 . NaOMe, MeOH,
RT
t -40°C -40°C
I C g H 1,3 H
CH2C12, NaF,
E t
-4OOC
*
F
1 .5h Barluenga, J. ; Rodriguez, M.A. ; Gonzhez, J.M. Asensio, G.
-
Tetrahedron Lett,
-78°C 2 n6uCECH
2 . Me2S,
4.
Hyuga, S.;
Br
\
/
I
c =c
/
\
Et
50%
: Campos, P.J.; (1986), 3, 3303
CH2C12
-
RT
nBu
0°C
3. EtCECEt, -78°C
\
Rajagopalan, S. Synthesis, ( 1 986), 480
I ( P Y ) ~ - B F ~NaH ,
1 . BBr3,
c =c
/
71 %
*
Brown, H.C. ; Bhat, N.G.;
Et-EC-Et
nPr ,
-
-
Dibal-H
b
Br
\
/
0°C
1 2 , AcOK,
THF
Takinami, S.: Hara, S.; Suzuki, A.
*
Chem Lett, (19861, 459 --
C=CH - C =CH E t
I
Et 74%
458 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
6
SECTION 372
C H I 3 , C r C 1 2 , 0°C
THF, l h
78%
*
Takai, K. ; Nitta, K.; Utimoto, K. J Am Chem ---SECTION 372: Ketone 0
-
Soc, (19861,
*
0 0 II II PhC -C Ph
ZnC12 t
2 . PPh3
PhCCl
108,7408
Ketone
1 . PhCHO,
I1
(E : Z- = 8 9 : l l )
3 . NaN(TMS)2
Anders, E. ; Gassner, T.
92%
---Angeu Chem Int Ed Engl,
(1983),
22,
619
tBuOK, THF -80°C NO2
Nakashita, Y.; Hesse, M.
Helv Chim Acta, (19831,
*
66,
85%
845
Ryu, I.; h d o , M.; Ogawa, A.; Murai, S. ; Sonoda, N. J Am Chem Soc, (19831, 9, 7192 ----
KETONE
SECTION 372
1. PhI(OAc)2,
-
EtOH
aq. Na2C03,
-40°C
*
Schank, K. ; L i c k , C.
9:l
* : Pete,
'0
74%
Ph
MeOH:Et20
63%
J.-P.; S c h o l l e r , D. J Org Chem, (19841, -
-70 2 . HC1,
* P. : Poirier,
2, 2355
CH2C12
- ooc
HOH
t
* --R. Bull Chem Soc Belg,
BF3.0Et2,
Duhamel,
*do
5h
1. tBuN=CPh,
Fuks,
4 59
Synthesis, (1983), 392
hv,
Baudoux, D.;
RT
2. 0 3 , CH2C12
0
Feigenbaum, A .
KETONE
7 5%
(19841,
Et20
-70°c J.-M.; Tavel, G.
Tetrahedron Lett, (19841,
93, 1009
68%
2,43
460 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CH2C12, Hunter, D.H.
* ; Barton,
-80°C
D.H.R.;
95%
Motherwell, W.J.
RhC1(PPh3)3
CH2C12,
* ; Ishiguro,
V
RT
Tetrahedron E,(19841,
cat.
S a k a i , K.
-
SECTION 372
RT
25, 603
6
*L ,,,$tl"'
"I,,
Me
0
2.5h
84%
Y . ; Funakoshi, K . ; Ueno, K . ; Suemune, H. Tetrahedron E ,(1984), 2,961
+ II
*
Mitani , M. ; Tamada, M . ; Uehara, S. ; Koyama, K. Tetrahedm Lett, (19841, i P r C0IIS n c B u 3 ,
PhCH3
H2CH2CCH3 71 %
25, 2805
1% PdCl 2 ( PPh3)2 1OO"C, 2 0 h
i -Pr
0 Verlhac, J.-B.;
Chanson, E. ; Jousseaume, B.
: Quintard, 26,
Tetrahedron E ,(19851,
J.-P. 6075
93%
KETONE
SECTION 372
-
KETONE
461
0 II 1 . MeCH=CHCCH3, TiC14 Ti(OiPr)4, C H 2 C 1 2 -95°C
OSiMe,
2 . aq. K2C03 Huffman,
* J.W. ; Potnis,
S.M.; Satish, A.V. J Org CWsi, (19851,
-
1 . tBuOCH(NMe2)2 55"C, 24h 2 . 02, h u , B A N T
C H 2 C 1 2 , -78
B A N T = &-acenaphtha1
b
Seyferth,
25°C
ene thiophene
Wasserman, H.H. ; Ives, J.L. Y
-
72%
+
2,4266
8 2%
J Org Che5, (19851,
2,3573
nBu2(CN)CuLi2/C0 THF, -110°C 90 m i n
* D. ; Hui,
0
1.
II Me2CHCCH2CH=CH2
R.C.
0
86% J kn then! Soc, (19851, g, 4551
----
C N E t
S n ( O T f )2
)
0
0
ti I1 Me2CHCCH=CH(CH2)3CCH3
CH2C1 2 y -45°C 2 . C H 2 = C H C C H 3 , -45°C
(g
II
Stevens, R.V.:
Mukaiyama, T.
0
Chenl Lett, (19851, 851
5 5%
462 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1 . CH2=C,
0 II PhCH =CHCCH
/p h
OTMS
, -78OC
SECTION 372
0 Ph 0 It I I1 CH3CCH2CHCH2CPh
TrCl 0 4 , C H 2 C 1 2. a q . NaHC03
92%
Kobayashi, S.; Murakami, M.; Mukaiyama, T. Chem Lett, (19851, 953
--
PhC1, reflux 24h
6
Gonzalez, A.:
Guell, F.; Marquet, J.; Moreno-Magas, M. Tetrahedron E,(19851, 3735
26,
1 . NaNH2, LBuONa 2 . MeSSMe
3 . CuCl2.Cu0, a c e t o n e H O H , 35OC, 3 0 m i n
C a d , M.C.: Cag;r&,M.C.; P.
80%
-
Caubere, P. Tetrahedron Lett, (19851, 26, 3103 Ndebeka, G.; Riondel, A , ; Bourgasser, P.: Caubere, Y
Tetrahedron E,(1984),
,OMe
1. HCrC(CH2)3CH=CH2
(C0)5Cr=C,
MeCN, 7 O o C CH3
Wulff, W.D.
81 % Y
2 . AcOH/HOH/EtOH
* ; Kaesler,
R.W.
*
a.
25,
32% Organometallics, (19851,
1551
4,
1461
KETONE
SECTION 373
- NITRILE
A m b e r 1 ys t A - 26 ( N O 3 - )
0
II
463
t
PhCCHPh P h H , r e f l u x , 2h I Br * Cainelli, G. ; Manescalchi, F.; Plessi, L. Gazz C h i m Ital, (19861, --( H M P A ) M o O ( O ~ ) ~ ,D C E
P h C=C P h
Hg(0Ac)2,
*
4 0 " C , 2h
0 II
PhC-CPh I1 0
80% 116,163
0 Pht-bPh 0
80% * Ballistreri, F.P.: Failla, S.; Tomaselli, G.A. : Curci, R. Tetrahedron Lett, (19861., 3,5139 SEICTION 373: Ketone
--
4= Fe(CO
l3
-
Nitrile
1 . LiCMe2CN, CO, THF -78°C 2 . C F 3 C O O H , -78°C
t
3 . CAN, a q . acetone
*
P CN
85%
Semelhack, M.F. ; Herndon, J.W.; Liu, J.K.
Organometallics, (
1 . Li(TMS)CHCN
T H F , -78°C
2. C s F , a q . MeCN
Tomioka, K.: Koga, K.
*
96% Tetrahedron Lett, (19841, 25, 1599
464 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
CH =C /
2
\
1 . LiCHCH3
CN
0
>
2. BnBr
NMePh
I
BnCCH 2CH2CHCH3
92%
3 . H30t
*
Ahlbrecht, H. ; I b e , M.
CN
II
I
CN
SECTION 374
Synthesis, (19851, 421
*
Nikishin, C . I . ; Troyansky, E . I . : Misintsev, V.V.; Molokanov, A.N.; Ogibin, Y.N. Tetrahedron G,(1 9861, 3, 421 5 SECTION
374: Ketone - Olefin -
For the oxidation of a l l y l i c alcohols t o olefinic ketones, see Section 168 (Ketones from Alcohols and Phenols). For the oxidation of a l l y l i c methylene groups (C=C-CH, + , see Section 170 (Ketones from A l k y l s ad Methylenes).
C=C-CO)
For the alkylation of olefinic ketones, see also Section 177 (Ketones from Ketones), and Section 74E ( A l k y l s from Olefins) f o r conjugate alkylations. 1 . PhSC1, 2. NEt3,
McKervey, M.A.
Et20,
0°C
>
&SPh
RT, o v e r n i g h t
* ; Ratananukul,
P.
Tetrahedron Lett, ( 1 9831,
75%
2, 11 7
SECTION 374
Br
KETONE
0 II HP(OEt)2, NEt3,
-
OLEFIN
465
RT
15h
(96
* Hirao, T. ; Masunga, T.;Hayashi,
K.;
4)
:
66%
* Ohshiro, Y. ; Agawa, T.
Tetrahedron E,(19831, 24, 399
0 O C C l , l h O, M
e
CH 2 = C \ SnMe3
Pd (Bn) ( PPh3 )2C1
*
q ) j - O M e
Soderquist, J . A . ; Leong, W.W.H.
Tetrahedron E,( 1 9831,
TMSo
86%
2,2361
OMe SnC14,
OTMS
Nakamura, E.; SiMe, 1
0°C
CH2C1
* Shimada, J.; Kuwaji'ma, I. JCS Chem Cam, (19831, ---
60%
498
*
Nakamura, E.; Fukuzaki, K.; Kuwajima, I.
J C S Chem C a m , (19831, ---
499
466 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
OM e
I MeC(CH2)3C02Me I OMe
0 1 I CH2=CHCHCH2C(CH2)3C02Me
1
EtCOOH
Ph
* : Lunt, S.R.
+
( 1 2)
0
II CH2=CHCHCHCCH CH2C02Me 1 (88) 69% Ph
120°C
I
24h
Daub, G.W.
SECTION 374
Tetrahedron Lett, (1983), 24, 4397
1 % RuC13*H20 2 30% H202,
RT
0
5h
* 90% Ito, S.; Aihara, K.; Matsumoto, M. Tetrahedron Lett, (19831, 24, 5249 2 [ c 1 c u I IO - C U I ' c 1 ]
t-Bu&-BU
*
MeCN
Capdevielle, P.: Maumy, M.
Tetrahedron=,
OTMS
t*Bu6 0
80%
(19831, 24, 5611 0
1 % Pd(OAc)2, dppe MeCN, r e f l u x l h 78%
Tsuji, J.*: Minami, I.; Shimizu, I. Tetrahedron
E, (19831, 24,
5635
SECTION 374
-
KETONE
0 II 1. i P r C C l ,
CH2C12
[ Z n / C u C l /CH2C1 2 / M e I ] 20°C
-
reflux
2 . 1M K O H , MeOH
OLEFIN
4 67
* @ 7 5%
*
Shono, T. ; Nishiguchi, I.; Sasaki, M.: Ikeda, H.; Kurita, M. J Org Chem, (19831, 48, 2503 ---
-
0 '02,
Ac20,
DMAP
Py, CH2C12,
Mihelich,
*
2h
* E.D. ; Eickhoff , D.J.
71 %
J Org
-
M e 2 C = C H B r , PhCH3
/OAC CH2=C \ Ph
PdCl 2 ( g T o l 3 P ) 2 Bu3SnOMe,
,
(19831,
Kosugi, M.; Hagiwara, I.; Migita,
II
PhCCH2CH=CMe2
* -T. Chem L e t t ,
MeCH=CHLi,
2h
Pet ether,
-3OOC
74%
(19831, 839
78%
*
Mukaiyama, T. ; Ohsumi, T.
-Chem L e t t ,
4135
0
100°C
30 m i n
48,
(1983), 875
468 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
1. EBuLi
0
2 . ZnC12, THF C H =C =CH OMe
R u s s e l l , C.E.;
t
II
3 . T o l - I , RT, 8 h PdC12(PPh3)2, D i b a l - H
4. aq. H Hegedus, L.S.
3h
________)
RT
-
reflux
CH2C1
-
NEt3,
*
Negishi, E. ; Miller, J . A .
0
II
MeCH=CHCCl
66%
J Am Chem Soc, (19831, _105, 943
2 EtA1C12, b i M e ,
C H 2 =CHC - TO1
t
*
SECTION 374
97%
THF, 6OoC 24h
---J Am Chem
54% Soc,
CH2=CHSiMe3,
CC14
A1C13,
30 min
50°C,
(1983),
105,6761
-4
K j e l d s g n , C.; Knudsen, J.S.; Ravn-Petersen, L.S.; T o r s s e l l , K.B.C. Tetrahedron, ( 1 983), 3, 2237
63%
SECTION 374
-
KETONE
6% Pd(PPh3)4, THF,
OLEFIN
469
3% dppe
h
RT, 4 h
Y t-Bu
*
Trost, B.M. ; S e l f , C.R.
y
S
i
M
e
,
1
--J Org
.
2 LDA,
65OC
2 . CC14,
77OC
*
p."
AcO
g H 1 1)
* Rautenstrauch, V.
0
l h
-J Org
Wilson, S.R. ; Price, M.F.
84%
2, 722
Chem, (19841,
P d C 1 2 ( M e C N ) 2 , MeCN AcOH,
2, 468
THF
-
-70
YYo 0 0
Chem, (19841,
bl%
*
8OoC
J Org Chem, (1984),
9, 950
73%
0
II CH3C-Co(C0)3
*
- C H 2 N 02, TH F / D M S O
8h
* Hegedus, L.S. ; P e r r y ,
R.J.
A
0
54% --J Org Chem, (1984), 9, 2570
470 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 374
-Jr
0 II 1 . MeOCH=CHCCH3, E t 2 0 R T , 24h 2. HOCH2CH2NH2,
I C g H 13
Molander, C.A.:
lh
*
c a t . C r ( C 0 ) 6 , 38h
tBuOOH, ref1 ux CH2C02Me
Pearson, A.J.
*
ICgH13
98%
Singarem, B.; Brown, H.C. J Org Chem, (1984), 49, 5024 ---
PhH
*Q
CH2C02Me
: Chen, Y.-S.:
HSU, S.-Y.; Ray, T. Tetrahedron L e t t , (19841,
" " 2 & 3
3KH
*
To1O2S3
7 5%
524
25, 1235
1 4 LiC1, DMSO 5OoC, 7 5 min
Denmark, S.E.
* : Harmata, M.A.
87%
Tetrahedron Lett, (1984),
25, 1543
1 . Me2CuLi, T H F
EtO
WoEt
-78"C, l h
3 . MeCNYre.f l u x
Marsi, M.; Rosenblum, M.
*
J Am Chem ----
52% Soc, (19841, 106, 7264
SECTION 374
e>
KETONE
-
471
OLEFIN
1 . Ts-CH2N=C
2 . LBuOK 3. BnBr
*
.
4 . H30t
53% Moskal, J . ; van Leusen, A.M. Tetrahedron Lett, (1984), 25, 2585 P h v HQC' N
0
Gordon, E.M. Sundeen, J.
N E t 3 / PhH
0
* ; P l u ~ ~ e J. c , ; Delaney,
90%
N.G. ; Natarajan, S. :
Tetrahedron g , (1984), 25, 3277 1. PhI,
nBuCZCH
0
0
26OC
CO,
Zn(Cu)
P d ( P P h 3 ) 2 C 1 2 , DME C p 2 T i C 1 2 , 6OoC, 4 h
0
*
II
P h C C H = CHnB u
2 . HOH
92% $4
Tamaru, Y.; Ochiai, H.; Yoshida, Z. Tetrahedron Lett, (19841, 3, 3861 1. K CO
-
-
BnC1, a c e t o n e 3'ref~ux
2 . 5 0 % a q . NaOH HOH/ E t 2O
k
P
Beraldi, P.G.: Barco, A , ; Benetti, S.; Pollini, G.P.:
V.
-
h 50%
Zanirato,
Tetrahedron Lett, (19841, 25, 4291
SECTION 374
472 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
C02CH2CH=CH2
MO(CO)~ PhCH3, r e f 1 u x 85%
*
Tsuji, J. ; Minami, I.; Shimizu, I. 1 . Pb(OAc)4,
Chem Lett, (19841, 1721
L n
PhH
reflux,
5 min t 2 . a q . NaHC03 1N HC1
3.
Nakatani, K.: Isoe, S.
*
69%
Tetrahedron E ,(19841,
1 . Me3SiCH2CH=CH2,
0
TiC14,
Ii
-40°C
0
CH2C12, 3 0 m i n
PhCH =CHCCH3 2 . HOH,
-4OOC
-
RT
II * PhCHCH2CCH3
1
CH2CH=CH2
80%
*
25, 5335
Sakurai, H. ; Hosomi, A . ; Hayashi, J.
Org Syn, (1984),
62,
86
Me3SnCH2CH=CH2, 25OC 0 6 a t m C O Y PPh3 II Me2C=CHCH2C1 tMe2C=CHCH2CCH2CH=CH2 1% PdC12(MeCN)2 CHC13,
48h
*
54%
Merrifield, J.H.; Godschalx, J.P.; Stille, J.K. organanetallics, (19841,
3,
1108
-
KETONE
SECTION 374
PhCH3,
Macomber, D.W.
*
100°C
Ph
Organometallics, (1984),
bBr
Ce13,
THF
PhCHO,
*
473
OLEFIN
RT,
3,
64%
1589
t
l h
90%
Fukuzawa, S. ; Fujinami, T.; Sakai, S. JCS Chem Comn, (19851, 777
---
-
1. nBu3Sn-CEC-SiMe3, 0
PdCl 2 ( PPh3 ) 2 , r e f 1 u x
II
nC6H1 3CC1
DCE
2 . THF, 3.
RT,
620"C,
6h
14 Torr
*
56%
Ackroyd, J.; Karpf, M.; Dreiding, A.S. Helv C h i m Acta, (19851,
---
R
CH3CCH=CH2
1. P h S e - B a PhCH3,
25"C, 2h
2.
iPrCHO
3.
Py, H 2 0 2 ,
0
-
0
*
II
338
OH
I
C H 3 C - CI t - C H i P r CH2
30°C
* -J Org Chem,
Leonard, W.R.; Livinghouse, T.
68,
71%
(19851,
50, 730
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
474
SECTION 374
0
II
EtCCHC02Me, CH = C
2 \
C ,H
I
Me
3
30°C
Me
C02Me
1 ,
I
CH2=CCH2-C-Cq
-
Et
P d 2 ( d b a ) CHC 1 M' e 0 92% II 12 min * o T s u j i , J. ; Shimizu, I . ; Minami, I.; Ohashi, Y.; Sugiura, T.; Takahashi, K. J Org Chem, (19851, 50, 1523 CH20COMe
-
-
1 . C1CH=CHC02H, OH
THF,
1
n 8 u C H C H =CH
65OC,
2 NaH
4h
2 . H 3 0t
*
0
II
nBuCH=CHCH2CH2CCH3
2 KH, 1 2 0 ° C * 6h Buchi, G. ; Vogel, D.E. J Org Chem, (19851, 3.
Negishi,
* E. ; Holmes,
OYP
58%
4664
62% S.J.; Tour, J.M.; Miller, J . A . ---J Am Chem Soc, (19851, 107, 2568
CH2=CHCH2Ti(NEt2)3 THF,
50,
-25OC,
15h
0
t
Ii
P hCCH 2CH = C H 2
95% Reetz, M.T.*;
Wenderoth, B. ; Urz, R . Chem Ber, (19851, --
e, 348
SECTION 374
-
KETONE
475
OLEFIN
tBuOOH, MeCN Cr(CO) r e f 1ux
Me C 0 2 M e Pearson, A . J .
* : Chen,
Me
C02Me
60%
Y.-S.; Han, G.R.; HSU, S.-Y.; Ray, T. JCS Perkin I , (19851, 267 ---
1. LDA,
THF
*
2.
12 BF3*OEt2
3.
5% Pd(PPh3)4,
CH2=CHCMe2N02, x
THF
"s"'/' 7 0%
RT
*
Ono, N. ; Hamamoto, I . ; Kaji, A. Bull Chem Soc Jpn, (19851, 58, 1863
----
cH
-
/
= c H C'H
HRh( PPh3)4,
0
- c H zc \
H
PhH,
105°C
*
0 18h II t CH3CH=CHCnC,H,
Sato, S.; Matsuda, I. ; Izumi, Y. Tetrahedron Lett, ( 1 9851,
-
8 CAN,
x
83%
26,
1527
25°C
5 0 % a q . MeCN
SiMe,
-
66%
Wilson, S.R. ; Zucker, P . A . ; Kim, C.-W.: Villa, C.A. Tetrahedron Lett, (1985), 26, 1969
476 CCMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 374
1. 2 nBu3SnCH2Li / 0 \ nPrCH-CHCCH3 -
*
I0I
THF,
-
-78°C
RT
nPrCH=CHCH2CCH3
2 . BF3-0Et2
Sato, T. ; Kikuchi, T.; Sootme, N.; Murayama, E. Tetrahedron Lett, (19851,
7 6%
26, 2205
PdCL2(PhCN)2 THF,
Clark,
* G.R. ; Thiensathit,
PH
OEt
I
nBuC5cCH-C-CH3
I
OEt
CH2C12,
CuBr, 3. Si02
2, 2503
NEt3
0°C
2 . 4 E t M g B r , THF
Bernard, D.; Doritheau, 0
67%
S. Tetrahedron Lett, ( 1 9851,
1 . MeS02C1,
II
t
reflux 2.5d
-30°C
nBu
*
-
E t
\
/
0
II
C =C=CHCCH3
68%
* A.
Tetrahedron L e t t , (1985), 26, 4923
-
0
C H I 2 - Z n Me3A 1
C H ~ C ( C H ~ ) ~ C H O THF,
25"C,
48h
I1
tC H ~ C ( C H ~ ) ~ C H = C H ~
* K. ; Nozaki,
Okazoe, T.; Hibino, J.; Takai, H. Tetrahedron L e t t , (1985),
96%
2, 5581
SECTION 374
KETONE
-
OLEFIN
477
MeCH=CHBr, C O Y 80°C P d ( P P h 3 I 4 , cBuOH 8h
Amari, E.; Catellani, M . ; Chiusoli, G.P. -J Organomet Chem, (1985) ,
-
0
0
I1
CH C H C C H C H 3 31 I Br Br
dioxane,
- Go
30 m i n
I))))
*
Joshi, N.N.; Hoffmann, H.M.R. Tetrahedron L e t t , (19861, 1 . 2 NaH,
II
2.
Ph3P=CHCC02Et
THF
CH2=CH(CH2)8CH0 cat.
2 . H30
Pietrusiewicz, K.M.*;
+
9, 383
, Zn/Cu, 10°C
TMS-C1
0
89%
HOH,
40°C
,I
(L:E
90%
P
3, 687 C02Et
(CH2)*CH=CH2
73%
= 9:l)
Monkiewicz, J. Tetrahedron L e t t , (19861,
27, 739
C H 2 = C H C H 2 0 A c , PhH
a z o o , Tsuda,
cat.
* T. ; Okada,
Pd(PPh3)4, 3h
RT)
* T.
M.; Nishi, S.; SaeguSa, -J Org Chem, (1986) , 2,421
93%
478 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
N a C H ( A c ) 2 , THF, 1 9 h
PhfHCH=CHPh
TiC,H,PdCl/L.
nn,
40°C
't
P h C H C H = CHPh
I
Hayashi, T , = ; Yamarmto, A. : Higihara, T.; I t o , Y. T e t r a h e d r o n L e t t , (1986),
-
Si02,
3, 191
sealed tube
60°C, 4h
*
SECTION 374
Me
HO
74%
Smit, W.A. ; Gybin, A.S.; Shashkov, A . S . ; gtrychkov, Y.T.: Kyz'mina, L.G.; Mikaelian, G.S.; Caple, R. ; Swanson, E.D. T e t r a h e d r o n Lett, (19861, 3, 1241, 1245
-
OH
I
CH2=CHCH20C02Me
CH2=CH(CH2)3CHCH=CH2 -CH2=CH(CH2)3CCH=CH2 R u H ~ ( P P ~ ~ ) ~ PhCH3, r e f l u x * Minami, I . ; Yamada, M.; T s u j i , J. T e t r a h e d r o n Lett, (1986),
-
1 . KH(12 p r e t r e a t e d ) 1 8 - c r o w n - 6 , THF _.____)
r e f l u x , 2h
apr 95%
3, 1805
2 . E t O H , -78°C 7 5% (improved procedure) * Macdonald, T.L. ; Natalie Jr., K.J.; Prasad, G.; Sawyer, J.S. JOrg-, (19861, 51, 1124
KETONE
SECTION 374
-
479
OLEFIN
0
I1 PhCCHN2, BF3*0Et2
MeCH = C H C H O H
RT,
Kachinsky, J.L.C.;
4h
* Salomon, R.G.
0
+
Hatanaka, Y.; Kuwajima, I.
i
k:H
I
Me -J Org Chem, (1986),
4h t
II
PhCCHCH=CH2 83%
51,
1393
63%
J Org Chm, -
(1986),
51,
1932
1. CH3CCH2CH2CHPhCOOH
2.
Ph
H
r e f l u x , 16h
LDA,
THF, -78°C
3 . Me1 4 , Red-A1 5 . Ht
Meyers, A . I .
t# 0
PhH,
t
Me
42%
(99.8% ee)
; Lefker, B.A.; Wanner, K.Th.; Aitken, R.A. -JOrg Chm, (1986), 51, 1936
-
OAC 1
C02CH2CH=CH2
?4
P d 2 ( d b a ) 3 .CHC1
PPh3,
CH3CN
t
Tsuji, J. ; Nisar, M.: Minami, I. Tetrahedron Lett, (19861, 3, 2483
480 COMPEM>IUM OF ORGANIC SYNTHETIC METHODS VOL 6
0 It CH2=CHCH20COCH2CH=CH2 (51e3
5% Pd(OAc)2,
*
5% dppe
MeCN,
30h
Minami,.I.; Takahashi, K.; Shimizu, I.; Kimura, T.
SECTION 374
Q
95%
-J w hJw Tetrahedron, (1.9861,
42,
2971
1 . LiN(TMS)2
2. 3.
PhCHO Me3SiC1
4.
5OOOC
Ph
hSiMe,
0
OSiMe,
2)
( 98
-
Tetrahedron Lett, (19861,
Bloch, R.; Gilbert, L.
1. tBuMe2SiOTf, -78OC PhCHO,
-78OC
-
RT
4 . HF, T H F / h e x a n e ,
* Kozikowski, A.P. ; Jung, 0
II
0°C
63%
J Org ---
S.H. 0 It
P h T l ( OCCF3)2
,
4% Li2PdC14,
*
PhCH=CHCCH3
25OC
1 .5h
J Org Chem, ---
-
Chem, (19861, 51, 3400
THF
5 CH3CCH=CH2
* Kjonaas, R.A.
3511
4,,
PPh3
2 . E B u L i , THF/hexane 3.
66%
27,
(19861,
51, 3708
98%
NITRILE
SECTION 376
-
48 1
OLEFIN
Reviews:
"Chromium (11) Reagents: Reduction of a-Acetylenic Ketones to trans-Enones"
*
Smith 111, A.B. ; Levenberg, P.A.: Suits, J.Z. Synthesis, ( 1986) 1 84
"Oxidation of Alkenes: Metal Induced Formation of an Allylic Carbon- Oxygen Bond"
Muzart, J.
*
Bull Chem Soc Fr, ----
SECTION 375: Nitrile
(19861, I165
- Nitrile
1 . L D A , P h H , 5"C, 1 5 m i n
NC
Br
3. H O H Br 4. 1 0 X p q . N a O H Davis, W.A.; Cava, M.P. --J Org Chem, (19831, 48, 2774
91 %
NC V C N
I
NaCH(CN)2y
CuI
HMPA, 12OOC
Suzuki,
* H. ; Kobayashi,
SECTION 376: Nitrile
-
T.; Osuka,
* -A. Chem Lett,
59%
(19831, 589
Olefin
*
Nishiyama, H.: Sakuta, K.; Osaka, N.; Itoh, K. Tetrahedron Lett, ( 1983)
2, 4021
482 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
0 CHO
1 . Me,C=C=NS
TMS'
TiC14,
SCN
iMe3
Ti(OiPr)4
CH2C1 -78OC 2. aq. Na2C03 3. B F 3 . O E t 2 , Okada, H.; Matsuda, I. ; Izumi,
Q
66%
2 y
1. LiCMe2CN,
-78
-
= 9:l)
(1983), 97
THF/HMPA 25°C
2 . CF3COOH, -78°C 30 m i n
* 85%
*
Semmelhack, M.F. ; Herndon, J.W. Organometallics, ( 1 983), 1. C02, Ca(OC1)2 CH2C12, HOH, 1 0 ° C 2. NaCN
3. B u 4 N I , HOH, l l O ° C 4. LBuOK, THF, RT
*
2,
363
- I'"
Suzuki, S. ; Fujita, Y.; Nishida, T. -Syn Comnun, (19841, 1
SECTION 376
FI
58%
fi, 817 CN
(Et0)2PCN, LiCN THF, RT, 5 m i n ~7
2. BF3*OEt2, PhH RT, 2 h
Harusawa, S.; Yoneda, R.;
* Kurihara, T. ; Hamada, Y.;
Tetrahedron L e t t , (1984),
80%
Shioiri, T.
2,427
SECTION 376
NITRILE
1. PhCH2Br,
-
483
OLEFIN
K2C03
acetone 2 . 5 % a q . NaOH
e
CH2=C
/
\
CH2Ph CN 50%
Baraldi, P.G.; Pollinj., G.P.; Zanirato, V . ; Barco, A . ; B e n e t t i ,
s.
0
Synthesis, (19851, 969
C S CH
OMe
Chatani,
TMS-CN , P'dC1 P y , PhCH3, r e f l u x 20h
* N. : Hanaf'usa,
T.
NC
'
c=c \
SiMe3
88% JCS Chem Comn, (1985), 838 ---
Me3S i C H 2 C H = C H 2
h v , MeCN, 4 0 h
66%
CN
Mizuno, K .
* : Ikeda,
M.:
*
O t s u j i , Y. Tetrahedron L e t t , (19851,
26,
461
Pd2(dba)3.CHC1 C02CH2CH=CH2
PPh3,
EtCN,
3h 81 %
r e f 1 ux
*
Minarni, I . ; Yuhara, M.; Shimizu, I . ; T s u j i , J. JCS Chem Comn, (19861, 118 ---
r
484 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
Miyake,
SECTION 377
R +FN CN
C02Me
TMS-CN,
RT
C02Me
______)
SnC14,
30 m i n
(2
CH2C1
* H. ; Yamamura,
CH2=CHCH2S i P h 3
C02Me
7
1 . PhCH=CHN02, T i C 1 4 C H 2 C 1 2 y -1 5 ° C 2. Zn, THF,
*
3,3025
Tetrahedron Lett, (1986),
K.
Uno, H. ; F u j i k i , S.; Suzuki, H.
65%
8,
CN
I
CH2=CHCH2CHPh
l h
*
6 9%
(1986) , 59, 1267
Bull Chem Soc JJJ, ---
- Olefin ---
SECTION 377: Olefin
1 . CBuLi, THF 78 " C
-
* CH2 CHCH=CHnC5H1
2. cC5H111 3 . 6 5 0 " C , 0.1 T o r r
Ls02
90%
Bloch. . . , R.:. Abecassis. J.: Hasson, D. .Can J Chem, (1984), 62, 2019 --Tetrahedron Lett, n 9 8 3 1 , Bloch, R . ; Abecassis, J.
2,1247
-
1. 2 LBuLi, hexane, CH2 =CHOE t
2 TMEDA -78°C
2 * ZnC12s T H F y -78-0"c
OEt
(L)
3 * ICH=CHnC5H1 5% P d ( P P h 3 ) 4 Negishi, E.*; Luo,
F.-T.
--J Org
I
CH2=C-CH=CHnC5H11 74%
Chem, (19831,
48,
1560
OLEFIN
SECTION 377
TMSO( CH 2 ) 6CECH
-
2 . aa. NaOH
3. E t C H = C H I
OLEFIN
485
H O ( CH2) 6CH = C H C H = C H E t
Pd ( P P h 3 )4 in PhCH 120°C 74% i n T H F 3: 65°C 74% Cassani, G . ; Massardo, P.; Piccardi, P .
(EE:ZE
=
99:i)
( E : E= 9 9 : l ) Tetrahedron Lett, ( 1 9 8 3 , 24, 251 3
n,
nC8H1 7 C H = C H ( CH2)7C02Me Villemin, D .
*
Me02(CH2)7CH=CH 1
______t
WCl,,u 80°C nC8H,, CH =CH S n M e 4 , 1 8 h 68% Tetrahedron Lett, (19831, 24, 2855 tBu
54%
t
CFCl
(77% eel Y Sakane, S.; Fujiwara, J . ; Maruoka, K.; Yamamoto, H. J Am Chem Soc, (19831, 2,6154 ---CHO
PI H
CH2=CHCHnC5H, CI
Pd(acac)*, PPh3* dioxane, reflux
* 70h Moreno-MGas, M. ; T r i u s , A. Bull Chem Sac Jpn, (1983), --
56,
2154
486 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
6
-6
1 . B r C H 2 S 0 2 B r , h v , - 1 5°C CH2C12, 2h 2 . N E t 3 , CH2C12, r e f l u x 3. L B u O K , T H F / t B u O H 0°C
* Block, E.*;
SECTION 377
74%
J Am Chem Soc, (1983), 105,6165 Aslam, M. Block, E . ; Eswarakrishnan, V. ; Gebreyes, K. Tetrahedron Lett, ( 1 9841, 25, 5469
_---
Me2C=CH)2CuLi
9
5
>-J
~ C 5 H l l E t 20/TH F 5% Pd(PPh3)4
1
*
Jabri, N. ; Alexakis, A.; Normant, J.F.
c
Hl + 1 2 5 H 11
/ (97
Bull Chem Soc Fr, ----
:
f
3)
94%
( 1 983) , 11321
CSC(CH2)3CH=CH2 1 . i s o o c t a n e
C Z C - TMS
cPco(co)6 r e f l u x , 97h
2 .CuCl - H O H N E t 3 , MeCN * Sternberg, E.D.; Vollhardt, K.P.C. --J Org Chem, (19841,
0 I
C02Me
CH2=CHCH=CHMe,
3,1564
-0
CH=CHCH=CHMe
NEt3
Pd(OAcI2, 100°C P ( g T o 1 )3, 1 5 h
SiMe,
71 %
C02Me (EE:EZ = 8:2)
- *Mitsudo, T.; Fischetti, W.; Heck, R.F. J Org Chem, ---
(19841,
3,1640
71 %
SECTION 377
OLEFIN
0
-
n C 7 H , 5MgBr
I1
CH2=C=CHCH20P(OEt)2
j
T H F , -25OC
*
487
OLEFIN
Ei7H1 5 C H 2 = C CH =CH
-
80%
Djahanbini, D. ; Cozes, B.; &re, J.
Tetrahedron, (19841, 40, 3645 L e t t , (1 984), 25, 203 Tetrahedron -
0-4 t h KFe- 1111 0 c l a0 °yC
\
t b u t y l phenol
lh
Laszlo,
* P. ; Lucchetti,
ECMe (CH2)4
Tetrahedron Lett, (19841, I _
25, 1567
Ph2PMe, - 2 0 ° C
I
C S C Me
4\
J.
77%
Cp2TiC1 2 , N a ( H g )
I
Nugent, W.A,
1)
(4
* ; Calabrese,
Benkeser, R . A .
J.C.
J Am Chem ----
Soc,
(1984),
106,6422
80%
1 . C a ( s a n d ) , LBuOH
.
2. EDA, fiBuNH2
T H F , 24h
* ; Laugal,
90%
J.A.: Rappa, A.
Tetrahedron L e t t , ( 1984),
25, 2089
488 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
SECTION 377
*e+? "'gH1 3
1 . MeCH=CHCH2A1 i B u 2
C1 2 Z r C p 2 , D C E
nC 6H 3 C ~ C H -
2 . H30t Miller, J . A . ;
Negishi, E.
PhCH=CHCH20Ac
(r)
-
-\
60°C
25)
(75
*
-
Tetrahedron Lett, (19841,
1 . 5% P d ( P P h 3 ) 4 , RT P P h 3 , NaBr, THF MeOH 2 . EBuLi 3. PhCHO -1 7'C-RT
60%
25, 5863
PhCH=CHCH2CH=CHPh 82%
(EZ:EE
*
= 79:21)
Tsukahara, Y.; K i n o s h i t a , H. ; Inomata, K . ; Kotake, H. --Bull Chem Soc (1984), 57, 3013
EtOCH2C=CCH20Et
LiA1H4,
s,
MgBr2
E t 2 0 , 35°C
Barbot, F.; Dauphin, R.; Miginiac,
* P.
t
57%
Synthesis, (19851, 768
0 I1
1 . Py, (EtO)*PCl O ' C , 2h
CH2=C=CHCH20Et
24 nB u
>
-
nBu 2 . CBuMgBr, CuI T H F , 0°C - R T 69% 12h Araki, S . : Ohmura, M.; Butsugan, Y. Synthesis, (19851, 963
H OCH C E C C H OH
SECTION 377
OLEFIN
* E . J . ; Desai, 0 II SMe 1
489
OLEFIN
1 . Ph3P=CHCH P h C H 3 , 23°C
Me CHO
Corey,
-
2. m c p b a , C H C 1 3 3. 50°C, 4h
65%
Tetrahedron E,(1985), 26, 5747
M.C. 0
I1
1 . CF3C)20,, C H 2 C 1 2 RT,
3h
2 . CH2=CHnC5H1 1 ,
ooc *
CH2=CHCH=CHnC5H1
C F 3 C O O H , 90 m i n 63% 3. m c p b a , C H 2 C 1 2 4 . 140°C I s h i b a s h i , H.*; Komatsu, H.; Maruyama, K.: Ikeda, M. Tetrahedron E,(19851, 26, 5791 CI
1. t B u L i , LBuOK
pentane/ hexane
2.
2 "C12H25Br THF,
Cordon 111, B.
Br
Engman,
lh
74% Mera, A.E.; Kumpf, R.J. --J Org Chem, (19851, 50, 1540
* : Blumenthal,
M.;
1 . N a B H 4 , MeOH 10%
Br
RT,
*
O - T e T e a
S
S
2 . HOH
* L. ; Bystrtim,
S.L.
93%
J Org Chem, (1985),
50, 3170
490 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6 1.
4
~-Bu
fl
P h'
BrCH=CHPh,
PhH
Pd(PPh,), r e f 1 ux
B/OQ '0'
Miyaura, N.:
-
t
-
2h
86%
*
Yamada, K . ; S u g i n m e , H.; Suzuki, A. ---J Am Chem Soc, (19851, 107, 972
P h C H = C H 2 , PhH -
RuCl 2 ( P P h 3 ) 3 1 5OoC
*
-Chem L e t t ,
Kamigata, N . ; Ozaki, J . ; Kobayashi, M.
1. nBu2CuLi
H C E CH
Taylor, R.J.K.
.
* : Burford,
n-Bu
71 % S.C.
Tetrahedron L e t t , ( 1 9851,
CuBr . S M e 2 , M e M g B r M e 2 S , Et20, - 4 5 ° C
n C 6 H 13CrCH 2 . C H 2 = C H C H 2 B r [Me2N],P=0, -30°C 3 . a q . NH4C1 I y e r , R.S. ; H e l q u i s t , P .
*
(19851, 705
w -
*
2 . Me1
1
-
-
* * B u s h
2 . NaOEt, E t O H ,
7
Furber, M.;
SECTION 377
E-
"'gH13
3rg Syn, (19851,
26,
3285
L/ 85%
64,1
SECTION 377
OLEFIN
-
die-/
1 . LiA1H4, 0°C - R T T, H 1F 8 h
*
2 . a q . NH4C1
3
Wang, K.K.
*
Epling, G.A.
491
OLEFIN
0°C ; Nikam, S.S.; Marcano, M.M.
WT3
--LJ
(E:I
= 4:l)
80%
6
-
Tetrahedron L e t t , (1986), 27, 1123 CN
@
, h v
CN
NaBH4, MeCN, H O H
* ; Florio,
*
H' Me
8h
Tetrahedron L e t t , (19861,
E.
27,
86% 1469
PhCHO, dioxane P h C H = C H C H 20H
Pd ( a c a c )
,
r e f 1 ux
PhCH=CHCH=CHPh
lllh 53% * Moreno-Makas, M. ; OrtGo, R.M.; Prat, M . ; Gal&, M.A. Syn Cornnun, (19861, 1003 --
16,
Tsuji,
* J . ; Sugiura,
66% T.; Yuhara, M.; Minami, I. JCS Chem Comn, (19861, 922
---
492 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 6
e-,
PhCH=CHCH2C1
nBu3SnC1,
5OoC
DMF
PdC12, P P h 3 , Et4NOTs,
SECTION 377
*
P
h
G
P
h
24h
Yoshida, J . ; Funahashi, H.; Iwasaki, H . ; Kawabata, Tetrahedron Lett, (1986),
* N.
92%
3, 4469
Reviews: V a t a l y s i s of t h e Cope and C l a i s e n RearrangementsTr Lutz, R.P.
* -Chem Rev,
(1984),
84,
205
IIMercury ( 1 I ) a n d Palladium (11) Catalyzed [ 3 , 3 ] - S i p a t r o p i c Rearrangement Overrnan, L.E.
*
Angew Chem I n t ----
Ed=,
(19841,
23, 579
lrAsymmetric Diels-Alder and Ene Reactions i n Organic Synthesis"
O p p l z e r , W.
*
Angew Chem Int Ed
---
x, (1984), 23, 876
IIAcetylene Equivalents i n Cycloaddition Reactions" DeLucchi, O . , Modena, G. I1IT 3-
Tetrahedron, (19841,
Allylpalladium Compoundsf1
J o l l y , P.W.
*
Angew --Chem I n t Ed
40,
2585
x, (19851, 24, 283
Compendium of Organic Synthetic Methods, Volume 6 Edited by Michael B. Smith Copyright 0 1988 by John Wiley & Sons, Inc.
AUTHOR INDEX Abbott, D.E.: 187 A h , K.: 129 A b e , N.: 141 Abecassis, J.: 484 Abeywickreq, A.N.: 202 Abidi, S.L. : 007 Abiko, A.: 010 Abla, M.A.: 399 Abou-hsali ,*M. : 166 Abrams, S.R. : 008 Achiwa, K.: 276, 362, 377 Acker, M.: 232 Ackroyd, J. : 473 Adak, M.W.: 055 Adam, W. : 328 Adamczyk, M. : 292, 31 0 Adams, B.!: 468 Adams, C. : 038 Addess, K.J.: 331 Adkins, R.L.: 165 Adlington, A.M.: 097, 234 352, 424 Aebi, J.D.: 296 Aerssens, M.H.P.J.: 290 Agawa, T.: 107, 157, 188, 215 221, 289, 418, 465 Ager, D.J. : 059, 271, 355 Agosta, W.C.: 41 1 Aguero, A.: 225, 444 Ahlbrecht, H. : 121, 369, 369 389, 406, 464 Ahmed-Schof i e l d , R : 390 Ahn, K.H.: 200 Aida, T.: 140 Aihara, K. : $66 Aitken, R.A. : 003, 479 Aizpurua, J.M.: 185, 187, 240 Akase, F.: 2g2 Akermark, B. : 158 AkgUn, E.: 356 Akiba, E.i 271 , 327 Akiba, K. : 286, 345, 369 Akita, M.: 232 Akiyama, T.: 431 Akutagawa, S. : 389 Alajarin, M.: 034, 149
*
.
A l b i m t i , K.F.i 369 Albright, : 340 Alexakis, A. : 073, 089, 173 220, 389, 454, 486 Alexander, R.: 175 Allwood, B.L.: 037 116 Almnd, M.R.: Alneri, E.: 176 Alpegiani& M . : 018, 185 Alper, H. : 081, 082, 104, 139 145, 153, 155, 156 162, 163, 195, 196 200, 226, 231, 280 Altnau, G.: 086 Aly, M.F.: 362 Amari, E.: 477 Ambler, P.W.: 293 Amita, F.: 383 AmmanamancQi, R.: 128 Amos, R.A. :,140, 179 Amouroux, R. : 426 Anciaux, A4J.: 093 Anders, E. : 215, 458 Anderson, K.W.: 188 Anderson, O.P.: 310, 365 Ando, K . i 246 Ando, M. : 044, 253, 433 453, 458 Ando, R.: 092, 095 Ando, S.: 416 Ando, T.4 189, 221, 287 Ando, W. : 332 Andreoli, P.: 109 Andrews, S.W.: 322 Andrianome, M. : 069 Angle, S.8.: 412, 420 Anker, D. : 166 Annunziata, R.: 310, 311 Antebi, S.: 145, 163, 196 Antonini, I.: 365 Antonsson, T.: 422 Anwar, S.: 307 Anwer, M.K.: 0i;l Anzeveno, P.B. : 401
J.1.
Aono, T.: 158 Aoyama, T.:
126
493
494
INDEX
AUTHORS
*
Appel, R. : 140, 353 Aquadro, R.E.: 019, 039 Arai, H. : 252, 309 Arai, I.: 096, 287 Araki, K.: 003 Araki, S.: 253, 488 Araki, T.4 196 Arase, A. : 139, 246, 289 Arcadi , A. : 348 Arcelli, A.: 022 Arhin, A , : 116 Amani, E.: 449 Arrhenius, P.: 173 Arrieta, A.: 240, 448 Arseni jevic, L.i 059 Arsenijevic, V. : 059 Arseniyadis , S. : 387 Arvanaghi, M.: 226, 435, 449 Arya, P.S.: 031 Aryal-KaloustiaQ, S. : 41 1 Arzoumanian, H. : 446 Asai, N.: 302 Asami, M.: 098, 141 Asano, S.: 105 Asensio, G.: 145, 457 Aslam, M.: 486 Aslanian, R.: 106 ASO, Y.: 135 Assercq, J.-M.: 173 Atherton, J.I.: 003 Atkins, R.K.: 317 Atkinson, 3.G.: 179 Atoh, A.: 391 Atsunori, M.: 031 AttenbacQ, H.-J. : 218 Au, A.T. : 215 Aubert, C.: 188 Auburn, P.R.: 423, 443 Avasthi, K.; 265 Awata, T.: 143 Axiotis, G.: 334 Ayaguchi, Y.: Ayorinde, F. 0.g481 86 Azadoni, H.N.: 060 Aznar, F.: 205, 390
BEbkvd.1, J.-E.
*:
125,106 415, 416
Baba, T. : 262 Babler, J.H. : 237 Baca, S.B.: 294 Bach, J.: 201 Bachand, C.: 123 Bachanova, k.A. : 276 Bache, M.D. :*421 Baciocchi,,E. : 394 Back, T.G. : 199 Bae, S.K.: 358 Bagheri , V. : 143, 206 Bailey, T.R.4 122 Bailey, W.F. : 074, 174, 396 Baillargeon, V.P.: 059, 060 Baizer, M.M.: 143, 401 Bajgrowicz, J.A.: 363, 376, 378 Baker, G.i 126 Baker, R. : 219 Balabane, M.: 125 Balasuhrmanign, T.R. : 408 Baldwin, J.C.,: 097 Baldwin, J.EZ : 234, 352, 424 Baleja, J.D. : 169 Balkovec, J.M.: 412 Ball, T.F.: 427 Ballistregi, F.P.: 463 Balme, G. : 185 Balogh, M.: 225 Balss, f . : 232 Ban, Y. : 107, 363 Banerjee, A . : 055 Banfi, S.: 430 Baraldi, P.G.: 483 Baralt, E.: 136 Baran, D.: 106 Barbaruah, M. : 154 Barber, Y.J.: 294 Barbot, F. : 488 Barcelo, G.: 136 Barco, A , : 475, 483 Barluenga, J . : 110, 145, 205 224, 251, 252 267, 370, 384 390, 448, 457 '
AUTHORS
INDEX
*
Barnette, W.E. : 400 Barrans Jr.: R.E.: 032 Barrette, E.P.: 209 Barrio, J.R. : 193 Barrish, J.C.: 308 Barry, C.N.i 166 Bartoli, G. : 228 Bartoli, J.F.:,177 Barton, D.H.R. : 029, 031, 115
123, 129, 167 181, 194, 196 234, 259, 385 386, 460 Barton, J.C.: 091 Bartroli, J.:,313 Bartsch, R.A. : 446 Barua, N.C.: 154, 252 Baruah, J.N.:*154, 385 Basavaiah, D. : 284, 288, 338 Basha, F.Z.: 116 Battioni, P.: 177 Batuah, J.N.: 047, 179 Baudin, J.-B.: 064 Baudoux, DI: 459 Baudry, D. : 256 Bauer, T.: $37 Bauld, N.L. : 094 Bay, E.:,119 Beak, P. : 132, 372 Beaudoin, S. : 265 Beaulieu, P.L.: 149, 231 Bechstein, U.: 244 Beck, A.K.: Becker, C.: Becker, P.N.: 375 Becker, R.: 036 * Beckwith, A.L.J. : 200. 202 Bedeschi, A.: 0 8, 185. Bednarski, #.: 60, 437 Beebe, T.R. : 1 5 Beers, S.: 2g4 Begue, J.-P. : 88 Behnke, M. : 087 Behrooz, H.: 03 Belanger, P.C.: 468 Beletskaya. 1.P : 001 , 156, 221
495
Bell, T.W.*: 231 Bellamy, F.D. : 133 Bellasoued, M.: 294 Bellesia, F.: Belletire, +J.LfS? 291 Bellus, D. : 154 Belmonte, F.G.: 249, 256 Benati, L.: 380 Bencini, E.: 156, 304 Benetti, S.: 4x1, 483 Benkeser, R.A. : 032, 249, 256
487
Bennetau, B.: 023, 041 Bennett, R.: 106 Beraldi, P.C.: 471 Bergbreiter, D.E. : 055, 125
*
183
Bereplan, R.C. : 375 Bernad, P.: 251, 252 Bernard, D.: 476 Bernard, M.: 264 Bernardinelli, C.: 372, 412 Bernheim, M.: 285 Berryhill, S.R.: 108
Bertolini, G.: 298 Bertounesqufi, E.: 294, 334 Bertz, S.H. : 032 Berube, D. : 384 B e s t m , H.J. : 222, 336 Bestre, R.D.: 148 Beswick, P.J.: 077, 216 Betschart, C.: 383 Bhmddl,
H.: 444
Bhat, K.S.: 166, 344 Bhat, N.C.: 002, 284, 288, 457 Bhatnagar, A.K.i 037 Bhatnagar, S.P. : 115, 120 Bhatt, M . V . : 033 Bhushan, V.: 144, 213 Bienz, S.: 109 Bigelli, C.: 218 Billedeau, R.: 364 Biller, S.A.:'16g. Billington, D.C. : 430 Billion, A.: 386 Billmers, J.M.: 333
496
AUTHORS
Bin Manas, A.R.: 061 Bischoff, J.J.: 174 Bisling, M.: 259 Blankenship, C.: 320 Blanton, J.R,: 183 Blechert, S. : 368 Bloch, R . i 480, 484 Block, E . : 486 Blodgett, J . K . : 116 Bloom, A.J.: 110, 278 Bloom, S.H.: 079, 262 B l u m , Y.:
082
Blumenkopf, T.A.: 324, 443 Blumenthal,, M.: 489 Boche, G. : 285 b d e n , E . P . : 418 * Boeckman Jr.: R.K. : 050 Boensmann, H.: 300 Bogardus, C.C.: 165 Bogavac, M . 4 059 Boger, D.L. : 094, 392, 395 Boivin, J.: 386 Boldrini, G.P.: 135, 319, 349 Bolesov, I.G,: 094 Bonadies, F. : 155 Bonavoglia, F.: 090 Bond, F.T.: 265 Bonde, S . E # : 073 Bonini, C. : 155 Borders, R . J . : 325 Borg, R.M.: 390 Borschberg, H . J . : 150 Borush, R.C.: 385 Bosch, E.: 421 BOSCO, M. : $28 Bosnich, B. : 423, 443 Bottaro, J.C,: 234, 352 Boudjouk, P. : 445 Boukouvalas, J.: 352 Bouquet, M.: 158 b u r d o n , F.: 145 Bourgasser, P.: 462 Boutin, R.H.: 116 Bovicelli, P . : 159 i3oyd, S.D.: 245 Boyer, B. : 026
INDM
Boyer, s.K.". 201 Brady, W.T.*I 431 Braga, A.L.: 005, 286 a r a i s h , T.F.: 050 Branca, S.J.: 416 Branchaud, B.P. : 137 Brand, M.: 1z8, 450 Brandsma, L. : 290 Brannfors, J.M.: 210 Braun, M. : 020, 332 Elremmer, M.L.: 371 Brena, F.K.: 408 IBridon, D. : 029 Brinkman, K.: 227 Brinkman, K.C.: 354, 441 B r i t t o n , T.C.: 295 Broadley, K.: 111 Brocksom, T.J,: 399 Brookhart, M. : 093 Brotherton, C.E.: 094 Brown Jr.: Q.B.: 177 Brown, C.A.,: 002 Brown, H.C. : 002, 016, 044 051, 062, 097 283, 284, 288 317, 319, 320 329, 344, 453 457, 470 Brown, J . D . : 217 Brown, L.: 143 Brown, S.L.: 016 Brownbridge, PI: 445 Brunelle, D . J . : 171 Brunet, J.J,: 011, 185, 249 Brunner, H. : 036 Brunner, R.K.: 150 B r u t t s , D.: g24 Bryson, T,A. : 325 Biichi, G. : $74 Bubnov, Y.N. : 347 Buchan, C.: 153, 156 Buchman, 0. : 292, 248 Buchwald, S . L . : 264, 268 Bugden, G.: 308 Buhro, W.E.: 095 Bumagin, N.A.: 001, 156, 221
INDEX
497
AUTHORS
Bumgardner, C.k.*: 355 Bunnelle, W.H, : 427 bunnett, J.F. : 225 Buntin, S.A.: 053 Burford, S.C.: 490 Burgess, K.: 270 Burk, R.M.: 131, 388 BUSS, A.D.: 257 Butlers, M.:,191 Butsugan, Y. : 253, 488 Bystrtjm, S..E.: 106, 415 Bystrtjrn, S.L.: 489 B y W , H . - S . : 061 Cabal, M..-P.: 390 Cabre, J . :,099 Cacchi, S. 202, 348 Cahiez, G.*I 208, 220, 454 Caillaux, B.i 368 Cainelli, G. : 028, 109, 135 183, 463 Calabrese, J .C : 487 Callen, G.R.: 342 Calzada, J.G.: 006 Campbell, J . A . : 401 Camps, P . J . : 145, 457 Canella, K.A.: 021 Capdevielhe, P.: 195, 208, 466 Caple, R. : 478, Caporusso, B.M. : 263 Capozzi, G. : 002 Cardellicchio, C. : 089, 209 Cardellini, t$.: 365 Cardillo, G. : 314, 332 Carini, D . J . : 2i4 Carless, H . A . J . : 429 Carling, R.W.: 421 Carlon, M. : 224, Carlsen, P . H . J . : 052 Carrnan, L.: 353 Caro, B. : 026 Caron, M.: 316, 329 Carpino, P . A . : 374 Carpita, A.: 001, 281 Carr, S . A . : 347 Carre, M.C,: 462 Carrie, R. : 130, 133
-
.
Cartaya-Marin, C.P.: 223 Casares, A q . : 087 Casey, C.P. : 180 Casnati, G. :,449, 485 Castaldi, G. : 015, 451 Castaneda, A.: 443 Castedo, L.: 368, Castelhano, A . L . : 364 Castellino, S.: 404 Castro, B.: 017 Castro, J.L.: 368 Catellani, M.: 477 Caton, M.P.k.: 424 Caubere, P. : 011, 082, 185 * 249, 462 Cava, M.P. : 397, 481 Cavicchioli, S.: 451 Cefelin, P. : 260 Celebuski, J.E.: 392 eervinka,+O : 037 Cha, J.S. :,051, 179 Chabaud, B. : 172 Chakraborti, A.K.: 010, 148 Chakraborty, T.K.: 144, 161 Chalais, S.: 078, 226 Chamberlin, A.R. : 079, 262, 265 Chamchaang, W.: 257 Champney, B. : 165 Chan, D.M.T.: 412 Chan, T.H. : 140, 314, 404 Chan, W.K.: 150 Chandran, R.: 055 Chandrasekaran, S. : 135, 144 160, 161, 213, 238 Chang, H . : 136, 321 Chang, H.S.: 104 Chang, Y.K.: 358 Chanson, E.: 460 Chantarasiri, N.:+257 Chaona, S.: 257 Chapman, D. : 087 Chapman, K.T.: 307 Chapuis, C.4 372, 412, 413 Charles, G. : 118, 137 Chastanet, J. : 1 1 8 Chatani, N. : 058, 483
.
,
498
AUTHORS
Chatterjee, S.: 206, 441 Chattopadhyay, S. : 178 Chatzilosifidis, I.: 227 Chaudhuri, NIC.: 339 Chawla, H.M. : 274 Cheik-Rouhou, F.: 350 Cheikh, R.B.: 392 Chen, B.: 125 Chen, C.: 040, 055, 423 Chen, C.-S;: 042 Chen, M.-HI: 306, 456 Chen, Q-Y. : 001 Chen, S.-F.: 392 Chen, Y.-S.: 470, 475 Chenard, B.L. : 008 Cheng, Y.-S.: 371 Chianelli, 3.: 171 Chiba, K.:,107 Chiche, L. : 376 Chihara, T.: 3QO Chikashita, H. : 065, 084, 086 Chimichi, S.: 336 Chiusoli, G.P.: 477 Cho, B.T.: 319 Choabouni, R.: 392 Choi, V.M.FI: 435 Chong, J.M. : 002, 250, 293 297
Chou, C.S.: 053 Chou, T. : g79 Chou, T.-S. : 106 Choudary, B.M. : 054, 210 Chow, M.-S.: 287 Chowdhury, P.K.: 047, 179 Choy, W.: 350 Christol, H.: 056, 172 Christy, M.R.: 310 Chu, M.: 117, 371 Chua, V.: 032 Chung, B.C.: 104, 176 Ciaccio, J.A.: 331 Ciattini, P.Q.: 202 Cinquini, M. * 310, 311 Citterio, A.*: 090, 313 Claesson, A.*i 077 Clarembeau, M.: 068, 166
INDEX
Claremon, DIA.*: 380 Clark, G.R. : 476 Clary, D.W,: 273 Claudi, F. i 365 Claus, P.K. : 351 Clausen, K.: 102 Clawson, L.: 264 Clift, S.M.: i 5 4 , 437 Clive, D . L . J I : 149, 231 Coates, R.M. : 352 Coelho, F.: 291 Cohen, M.J.: 403 Cohen, T. : 432 Cole, E.R.: 148 Cole, T.E.: 002 Collington, #.W.: 049 C ~ l l ~ mD.B. , : 151, 265, 309 Colombo, L . : 298, 310 Colon, C. : 126 Colonna, S. i 430 Colvin, E.W. : 100 Comasseto, J . V . : 005, 286 Cominelli, A#: 090 Comins, D.L. : 028, 217 Concellon, J.M.: 251, 252, 267 Concepcion, J. I. : 182 Conley, R:A.: 393 Contento, M.: 109, 183 Contreras, R . : $21 Cooke Jr.: M.P. : 042, 087 Coombs, W.: 030 Cooper, A . J . L . : 304 Cooper, M.S,: 134 Corey, E . J . : 048, 091, 152, 169 209-, 235, 393 394, 438, 489 Cormons, A. :,373 Cornelis, A. : 078, 225, 226
-
273
Correa, I . D . : 429 Corriveau, J.: 172 Cortes, D.A.: 053 Cossec, B.: 376 Cossio, F.P.: 054, 209 Cottrell, D.A.: 101 Courtois, G I : 381
INDEX
Cousse, H,:
499
AUTHORS
426
D.P. : 190 Comes, B.: 487 cozzi, F.: 310, 311 Crabtree, R.H. : 082 Cramer, C,J.: 162 Crank, C. : 1 4 i Crawford, R . J . : 301 Crews, A.Q.: 126 Crich, D. : 181, 194, 196 Crisp, C.T.: 2Q2 Cristau, H.-J. : 056, 172, 376 Croft, A.P.: 446 Cronin, P.L.E.: 116 COX,
Cruz, A. : 408 Cuella, L.r 121 Cuervo, H. : 384
Cullin,,D.: 224 Cum, C. : 006 Cumins, C.H.: 352 Curci, R.: 463 Curran, D.P.=: 306, 333, 429 456
C z a r k i e , D. : 082D'sa, A.: 326 D'Angelo, Jc : 059 D'Incan, E. : 026, 222, 269 D'Onofrio, F.: 252 Da Settimo, F.: 263
Dabbagh, G.: 032 Dahan, N.: 049 Dalcanale, E. : 010 Dalpozzo, R.: 2$8 Danheiser, R.L. : 019, 034, 284 306, 373 432 Danishefsky, S. : 101, 360, 430
Daniewski, W.M.i
437 Dankwardt, J.W.: 027 Danson, L.: 024 Dao, T.V.: 019, 039 Dappen, M.S.: 162,
Darensbourg, M.Y. : 040 DasGupta, 8 . : 359 Daub, C.W. 424, 466 Dauben, W;G:*: 087
.
Dauphin, B.: 488 Dave, P.: 061 Daves Jr.: G.D.*: 168 Davidson, A.g.: 030 Davies, F.A.,: 114 Davies, S.C. : 016, 11 1, 163 170, 171, 227 It
262, 293, 306
Davis, A.P.,: 307 Davis, F.A. : 178, 333, 335 Davis, H.B.: 210 Davis, M.W.: 082 Davis, W.A.: 481 Dawe, R.D.: 329 De l a Pradilla, R.F.: 399 De Buyck, L . i 381 De Kimpe, N. : 130, 381 De Lornbaert, S.: 148 De Maldonado, V.C.: 257 De Poorter, B.: 177 De Souza Barbza, J.C. 089 De Vega, M.J.P.: 149 De VOS, M.J.: 022, 095 Deardorff, D.R. : 326 Degani, I.: 171 Degl'Innocenti, A. : 336 Delaney, N.g.: 471 Deleris, C. : 269 Dell'aira, D.: 394 Dellaria, J.F.: 295
,
Delrnas, M. i 253, 350
Delrnond, B. : 069 Delorme, D. : 046, 265 Delpeuch, J.-J.: 133 Dernailly, G.: 174 Demonceau, 8 . : 093 Denis, J.M. : 123 Denis, J.N.: 182, 193, 258 Denmark, S.E. : 162, 470 Depres, J.-P.: 291 Dequeil-Castain6, M. : 040 Des Abbayes, H. : 013, 221 Desai, M.C.: 002, 489 Desai, R.C.: 151 Deschamps, P. : 01 2 Deschenaux, R.: 085
500
Demotes, G . : 020 Deshayes, H.: 198
Deshmukh, M.N.: 276 Desmond Jr. : R.W. : 422 Desmnd, R . : 087 Despeyroux, B.: DeBernardis, J.F!'g 116 DeLuca, O.D.: 019, 039 DeLucca, G. : 187 DeLucchi, 0.: 492
DeRenzi, A.4 343
DeShong, P. : 1 6 1 , 378 Diab, J.: 166 Dickerhof, K.: 003 D i e t e r , J . W . i 4114 Dieter, R.K. : 174, 414 D i e t z , M.: 369, 406 Dilworth, B . M . : 429 D i t r i c h , K.: 334 D i t r i c h , L.: 033 D i x i t , V.: 281 Dixon, B.R.: 392 DiFabio, R.: 155 DiFuria, F.: 2z6 Djahanbini, Q. : 487 D j u r i i , S.W. : 105 DBtz, K.H.: 271 Doi, J.T.: 180 Dolan, S.C.: 196 Dolence, E.K.: 310 Dollinger, H.: 121, 389 Dornek, J . M . : 096 Donnelly, K.D.: 446 Dordor-Hedgecock, I . M . : 293 Dordor, I . M . : 293 Doria, G . : 082 Doritheau, A. : 476 Dorow, R.L.: 095, 295 Dorsch, D.: 150 Dossena, A. : 449 DOW, R.L.: 143, 313 Doyle, D.L.4 230 Doyle, M . P . : Q95, 143 Dreiding, A.S. : 473 Dresely , S . :,348 Drewes, S.E. : 417 Drozda, S.E.: 075
AUTHORS
Dua, 5 . K . :
INDEX
031 072 Dubois, J.-E. : 294, 334 Dudf i e l d , P. : 089 DuSlos , A. : 426 Dufresne, C.: 068 Dufresne, Y,: 046 Duhamel, P. : 351, 459 Dumont, W.: 193 Dunach, E.: 276, 277 Duncan, M . P . : 335 Dunlap, N . K . : 405 Dunn, B.S.: 346 Dunogues, J. : 023, 041, 269 Dupuis, D . : 372, 413 Dupuy, C . : 089 Duraisamy, M. :,238 Duthaler, R.O. : 403 Dzhemilev, U.M.: 034, 083 Eapen, K.C.: 074 Eberlein, T.H.: 444 Edstrom, E.D.: 178 Edwards, P.D.: 122 Ehrenkauf'er, R.E. : 135, 378 Eickhoff, D.J,: 467 E i l b r a c h t , P. : 232 Einhorn, J.: 060, 107 E i s , M . J . : 430, 123 Eisch, J.J. : 031, 264 E l Gharbi, R.: 350 E l Hallaouri, A.: 363, 378 El-Abed, D.: 303 El-Telbany, F.: 027 Eliasson, K.M.: 014 E l l i o t t , J.: $58 E l l i o t t , J . D . : 031, 282, 292 435 E l l i o t t , R . : 282 E l l i o t t , R.L.: 306 Elofson, R.M.: 124 Elsevier, C.J.: $49 Elshaf'ie, S.M.M. : 149 Emblidge, R.W.: 14G Ehda, J . : $82 Enders, g. : 353, 402 Endo, T. : 196, 248
Dua, S.S.:
INDEX
501
AUTHORS
Engel, N.i 300 Engel, R. : Engler , T. 4. 424 Engman, L. : 271, 489 EYholm, E.J.: 390 Enner, B.: 254 Ehterzari-Moghadgam, M. : 21 4 Ephritikhine, M. : 256 Epling, G,A. : 491 Erdik, E. : 097 Erickson, W.F.: 083 Ermolenko, M.S.: 218 Ernst, A.B.: 410, 419
Fernandez-Simon, J.L. : 267 Fernandez, H.: 121 Ferraboschi , P. : 060 Ferrera, L. : 370 Ferroud, D.: 319 Ferroz, H.MIC. : 399 Fetizon, M. : 049 Fiandanese, V. : 089, 206, 209 Fiaschi , R. : 447 Fieehter, A,: 318 Fiegenbaun, P.: 254 Field, L.D.: 192, 246 F i e l d s , K.1.: 152 Ertas, M.: 335 Fife, W.K. : 385 Escoula, B.: 189 F i l i p p i n i , L.: 312 Eswarakrishnan, V. : 486 F i l i p p o Jr.: J.S. : 146 Etinger, M.Yu.: 347 F i l l e r , R.: 452 Eto, H.: 412 F i n e t , J.-P.: 167 EtteP, J.B.: 04.j F i n k , D.M.: 306 Evans Jr.: S.A. : 166, 167 Finkler,,S.H.: 218 Evans, D.A. : 081, 295, 307, 313 Finn, J. : 333 Evstigneeva, R.P.: 052 Finn, M.C.: $25 Fiorenza, M. : 229, 313, Ewing, J.C.: 346 .. 315 Exon, C.M.: 325 236 Firouzabadi, H. : 053, 054, 056 Eyman, D.P.: 051 Fabryova, A,: 037 211, 213, 214 Fadel, A, : 253 Fischer, H. : 170 Failla, S. :,463 Fischetti, W.: 387, 486 FdLCk, J.R. : 185, 349, 439 Fishel, D.k.: 014 Falmagne, J.-B.: 297 Fitjer, L. : 266 Falter, W.: 424 F i t z , T.: 330 Fankhauser, J.E.: 295, 372, 374 Fitzner, J.N.: 295, 363, 372 Farooq, 0.: 244 374 Fauvarque, S.-F.: 013, 260 Fleischmann, M. : 110 Fazio, M.J. : Fleming, I. : 045, 070, 092 Feigenbaum, A. 'P2459 258, 402, 438 Fekarurhobo, C.K.: 429 Fleming, J,A.: 267 Fekih, A,: 031, 123, 259 Flinch, H; : 049 Felkin, H.: 256 F l i p p i n , L.A.: 319 Felman, S.W.: 437 Flood, L.A.: 043, 158 Fengl, R.W.: 163 Flores, H. J. : 408 Fenk, C . J . : 333 Florez, J.: 224 Ferguson, G.S.: 346 Florio, E.: 491 Fergusson, S.8.: 155 Flynn, D.L.: 295 Feringa, B.L. : 355 Foa, M.: 013, 156, 304 Fernuldes, J.B.: 068 Fobare, W.F., 317, 384, 388
?'
*
~
*
~
502
INDEX
AUTHORS
Fochi, R.: 171 Foglio, M.: 018 Fomani, M.: 451 Forcellese, M.L. : 159 Ford, W . J . : 264 F o r t , Y.: 082 Fortgens, H.P.: 373 F o r t i n , R.: 048, 165 Foucaud, A. : 096 Fournet, C. :,185 Fowler, F.W. : 117, 317, 371 Francalanci, F.: 013, 156, 304 Francisco, C.G.: 182 Frank, R.K.: 361 F r a z i e r , J.: 317 Freerksen, R.W.: 231 F r e i r e , RI: 182 Frejd, T. : F r e n e t t e , R . f 7 I 65, 382 Freudenberger, J.H.: 255 F r i e d r i c h , E.C. : 096, 187 F r i o u r , G.: 248, 220 F r i s t a d , W.E. : 067, 161, 162 195, 393, 410
419, 446
Fry, M.A.: 195 Fuchigami, J . : 143 Fuchs, P.L. : 050 Fuentes, L.M.: 119 Fugami, K.: 263 F u j i i , K.: 014, 219 F u j i i , S.: 058, 484 Fujimoto, K. 029 Fujimoto, Y.i: 428 Fujinami, T.: 153, 160, 473 Fujisaka, S.: 015 F u j i s a k i , S.: 116, 144, 172
*
366
Fujisawa, T. : 008, 020, 051 068, 184, 207 234, 250, 341 416, 425 F u j i t a , E . i 359 F u j i t a , E. : 212, 267, 357 F u j i t a , M.: 311, 315, 351 F u j i t a , Y.: 360, 482
Fujiwara, I.: 172 Fujiwara, J.: 038, 122, 485 Fujiwara, T.i 246, 327, 433 Fujiwara, Y. : 070, 342 Fujiyama, R.: 452 Fukagawa, T. : 342 Fuks, R. : 259 Fukuda, Y. : 283 Fukui, M.: O!#3 Fukmoto, K. : 103, 119 Fukutani, Y.i 096 Fukuyama, T. : 049, 361 Fukuzaki, K . i 465 Fukuzawa, S. : 153, 160, 260
*
447, 473
Funabiki, T. ,239, 243 Funahashi, H.: 492 Funakoshi , K. : 460 Funakoshi, Y.: 242 Fung, A.P.: 108, 192, 246 Furber, M.: 490 Furukawa, H. : 438 Furukawa, Y. : 400 Furuta, K.: 170, 283 Fustero, S.: 384 Gadallah, F.F.: 124 Cadras, A , : 269 Gagnier, R . f l . : 074 Gais, H.-J. : 142 Galamb, V. : 280
Galan, M.A.: 191 Gallagher, T. : 379 G a l l i , C . i 225 Gallo, R. : 006, 012 Gallos, J.: 156 Gamboni, R.: 323 Ganboa, I,: 448 Ganem, B. : 030, 123, 134, 259 Ganguly, A. : 440 Ganushchak, N.I.: 400 Garcia F r a i l e , A.: !#56 Garcia Martinez, A. : 080, 456 Garcia, J.: 099 Card, G.L.: 210 Gardano, A.: 013, 156, 304 Gardrat, C.: 225
INDM
G a r i g i p a t i , R.S.: 381 Garland, R.4 404 Garst, M.E. : 173
Gartiser, T.: 133 Gasc, M.B.: 132 Gaset, A.: 2534 350 Gasparrini, FI : 237, 275, 276 Gassmn, P.G. : 316, 330 Gassner, T.: 215, 458 Gaudino, JI: 405
Gaus, P.L.
503
AUTHORS
-
: 020
Gauthier, J.Y. 030, 145 Gebreyes, K.: 4 i 6 Gee, S.K.: 019
G e l l e m n , B.J.: 446 Genet, J.P. * 125, 379 Gennari, C.": 298, 310, 411
George, J.: 135 Georgiodis, G.M.: 041 Gerdes, J.M4: 087 Gerlach, H. : 015 Germon, C.: 389 Gerstmns, A.: 078 Gervais, C.: 166 Ghadiri, M.Ri: 083, 290 Ghatak, U.R. : 010, 148, 359 Ghelfi, F.: 452 Ghirlando,,R. : 383 Ghosez, L. : 101, 148 Ghribi, A.: Giacanelli, 282 Giacomini, D. : 109 Giang, Y.F.: 431 G i a n g i o r d p o , M.A. : 1 1 4 Giese, B. : 016, 057, 097, 160 Giesema#n, G. : 105 G i l , G. : 354 G i l , J.B.: 152 G i l b e r t , J . C . : 357 Gilbert, L.: 480 Gilbertson, S.R.: 321, 442 G i l l a r d , J.W.: 048 G i l l e s p i e , D.G.: 005 Gilman, J.W.: 410 Ginos , J. Z :,304 Giordaro, C. : 015, 451
A?:
.
Giovannini, F.: 318 Giovannoli, M.: 237, 275, 276 Givre, S.: 374 Gladysz, J . A . : 354, 441 Glens, Y.-F.: 392 Glue, S.E.J.: 236 Gnevasheva, L.M.: 432 Codel, T.: 089, Godleski, S.A. : 437 Godoy, J.: 052, 275 Godschdlx, J.P.: 472 Goering, H.L. : 070 Goh, S.H.: 200 Golebiowski, A.: 437 Gonzalez-Nunez, C : 1 45 Gonzalez, A.: 054, 209, 462 Gonzalez, J.M.: 457 Gopal, M.: 200, 280 Cora, J.: 057 Cordeev, K.Yu.i 052 Gordon 111, : 489 Gordon, E.M. : 471 Gordon, H.J.: 382 Gore, J.: 185, 387, 487 Gore, M.D.: 364 Goto, K.: 337 Goto, T.: 240 Gotoh, Y.: 341 Cotor, V.: 384 Could, T.J.: 294 Govindan, S.V. : 093 Gowriswari, V.V.L. : 338 Graff, M.: 420, Gramain, J.-C. : 363 Gramatica, P.: 233 Grandi , R.4 452 Gravel, D. : 065, 238 Greck, C.: 1 2 4 Greene, A.E. :,291 Greenlee, W.J. : 296 Greenspoon, N. : 086 Grehn, L.: 138 Grey, R.A.: Gribble, G.WZ'7 021, 241, 327 Grieco, P.A. : 295, 317, 384
.
8.
388
504
Grierson, D.S.: 133 Griesbeck, A.: 328 Grift%, 3.H.: 095, 260 Grigg, R. : 061, 362 Grigor'eva, #.Ya. : 197 Grimaldi, J. : 373 Grim, E.L.: 152 Gringore, O.H.: 299 Gross, A.W.: 394, 438 Grote, J.: 427 Groult, A,: 314 Groves, J.T.,: 177 Grubbs, R.H. : 207, 264, 268 Gruber, J.M.: 392 Grundkq, G.: 450 Giiell, F.; 462 Gu, X.-P.: 434 Guedin-Vuong, D. : 287 Guerrier, L. : 133 Guette, J.P.: 158 Guggenheim, T.L. : 137 Guillemin, J.C.: 123 Guinamant, J.L.: 401 Guindon, Y. : 029, 046, 048 049, 165, 179 Guixer, J.: 430 Gulevich, Yu.V.: 156 Gull, R.: 377 Gunnarsson, K.: 138 Guo, M.: 413 Gupta, A.K.: 317 Gupta, B.G.BZ: 189, 191 Gupton, J.T. : 106, 126 Gurmni, F.: 015 Guseva, S.A.: 016 G u t t i e r i , M.J.: 198 Guy, A.: 158, 314 Gybin, A.S.: 478 Gyoung, Y.S.: 022 Hzssig, 4.: 439 Haas, A. : 186 Haberman, L.M.: 316 Hackett, S.: 147 Hafeli, 1.K.: 037 Haga, K. : 124 Hagenak, J.A.: 301
AUTHC&S
INDEX
Hagihara, T.: 261 , 478 Hagiwara, I. : 228, 467 H a h n , C.S.: 338, 358 H a h n , G.: 22$, 282, 323, 339 Haines, S.R. : 170, 428 Hajipoor, Q.: 053 H ~ U , S.S. :*131 Hallberg, A. : 263 Hallock, J.S.: 151 Hamachi, I#: 34.1 Hamada, T. : 014 Hamada, Y.: 107, 157, 482 H m t o , I.: 269, 270, 349 412, 475 Hamamto, J . : 180 Hamana, H. 024, 335 Hamarfa, M.*(I 235 H m t a n i , T.: 013, 285, 342 Hamel, N.: 153, 156 Hamel, P.: 382 Hammond, G.B.: 224 Han, G.R.: 475 Hanaf'usa, T. : 189, 483 H a n w t o , T.: 305, 313 Hanazaki , Y. :,135 Hanessian, S. : 046, 265 Hanna, I.: 049 Hannon, F.J.: 091 Hansen, H.-J.: 169, 417 Hanson, R.M.: 325 Haque, M.S.: 004, 058, 152 335, 450 Hara, K.: 009 Hara, M.: 230 Hara, S.: 354, 455, 457 Harada, J.: 303 Harada, T.: 032, 093, 271 327, 341, 443 Harano, Y.: 107, 157 Harigaya, Y.: 396, 427 Harmata, M.A.: 470 Harnisch, HI: 016 Harpp, D.N. : 035, 140 Harre, M.: 404 Harris, F.L.: 418 Harrison, LW.: 415, 439
505
AUTHOpS
INDEX
Hart, D.J.*: 1 1 4 Hartmann, H. : 306 Hartner Jr.i F.W. : 437 Hartwig, W. : 197 HaruSawa, S. : 482 Haruta, J.: 159, 336 Haruta, R.: 283 Harvey, D.F.: 430 Haaegawa, M.: 339 Hasegawa, T.: 216 Hashimto, H.: 070, 201 Hashimto, K.: 212 Hashimto, S.: 376, 383 Hasimoto, H.: 255 Haaskerl, T.: 160 Hasson, D : 484 Hata, K.: 212 Hatanaka, Y. : 342, 479 Hatano, M.: 253 Hatayama, Y.: 170 Hauptmann, S. : 108 Havens, N.: 140 Hayama, T.: 297 Hayami, J.: 412 Hayashi, H.: 334 Hayashi, J. : 064, 237, 472 Hayashi, K. : 270, 338, 465 Hayashi, N. 456 Hayashi, T. : 023, 075, 261 299, 341, 341 Hazra, B.: 055 He, G.-X. ;,078 Heaney, H. : 134 Heasley, G.E. : 447 Heasley, V.L.: Heathcock, c . H . ? ~ ~ I324 ~, Hebel, D.:*191 Hebert, E.*: 234 Heck, R.F. : 453, 380, 387, 486 Hegedus, L.S. : 365, 454, 468 * 469 Heilmann, S.M. : 168 Heimbach, H.: 227, 404 Hellwig, G. :,216 Helmchen, G. : 088, 146, 150 306, 320
.
*
Helquist, P. : 227, 490 Hembre, R,T.: 155 Henin, F. : 374, 423 Hennequin, L.: 451 Henning, R.: 045 Henzen, A . V . : 436 Hernandez, D. : 258 Hernandez, R. : 182 Herndon, J.W.: 413, 463, 482 Herranz, E.: 312, 314 Herrera Fernandez, A . : 080 Herrick, J.J.: 028 Herrmann, R.: 2$2 Hershberger, J. : 088 Hershberger, S.: 088 Hershberger, S.S.: 073 Hertel, G.R.: 106 Herzig, JI: 440 Hesse, M. : 109, 158, 403 409, 458 Heuckeroth ,,R .O : 1 19 Hemann, A. : 158, 422 Heveling, J. : 081, 195 Heyn, A.S.: 083 Hibino, J . : 478 Hickmott, P.W. : 392 Hidai, M.: 2&2 Hiegel, G.A.,: 450 Hiemstra, H. : 102, 371, 373 Higashimura, H. : 394 High, J.: 224 Higuchi, K.: 207 Higuchi, N.: 309 Higuchi, T.: 075, 321 H i i , P.S.: 165 H i k i m a , H.: 318, 330 Hild, W.: 332 H i l l , C.L. 177, 178 H i l l , J . G . : 325 Himlsbach, R J. : 063 Hirakawa, g.: 327 Hirama, M. : 318, 366 Hirano, M.: 211 Hirao, A.: 036, 038 Hirao, I.:. 030, 285, 288, 393
.
.
.
506
AUTHORS
Hirao, T.*: 107, 157, 188, 215 221, 289, 418, 465 Hirashima,,T.: 057, 344 Hirobe, M. : 321
075 311, 315, 341 342, 405 Hiyoshi, T.: 135 Hodge, P. : OQ4, 183 Hoffman, R.V. : Q58 Hoffmann, H.M.R. * 055, 477 Hoffmann, H;M.g.*i 477 Hoffmann, R.W. : 024, 033, 334 * 348 Hojo, M. : 028, 065, 394, 398 Holman, N.J.: 170 Holmes-Smi th, R. : 256 Holmes, A.B. : 421 Holmes, 2.J.: 474 Holy, N. : 136 Holzapfel, W.: 218 Homoto, Y.: 032 Hong, C.Y.: 200 Hoole, R,F.A.: 417 HOOZ, J. : OOQ Hopkins, P.R. : 295, 363, 372 374 Hori, Y.: 290,,423 Horiuchi, C.A. : 302 Horler, H . : 057 Hormi, O.E.O.: 366 Horne, D.: 405 Horne, S.:,364 Horner, L. : 003 Hoshi, M. : 139, 246, 289 Hoshino , M. :,411 Hosokawa. T. : 355 Hosomi, A.: 044; 064, 237 377, 430, 443 453, 472 Hotchkiss, L.M.: 049 Hotta, Y.: 023 HOU, K.-C.: 333 Houpis, 1 . N . i 042 Howard, A.S. : 383 Hrubiec, R.T.: 126, 182, 261 Hirotsu, K.:
Hiyama,.T.*:
INDEX
HSU, M.H.: 415 HSU, S.-Y.: 470, 475 Htillmann, M.: 025, 041 Hiherbein, J. : 140 Hua, D.H.: 048 Huang, S.$B.: 206 Huang, Y. : 055, 359, 419, 425 Huang, Y.Z.: 040 Huber, I.: 101 Hubert-Habart, M.: 241 Hubert, A.J.: 093 Hubert, T.D.: 051 Hubner, F. : 227 Huckstep, M.Q.: 424 Hudlicky, T. : 093, 353 Hudrlik, A.M.; 441 Hudrlik,,P.F. : 441, 454 Huet, F. : 356 Huf'f, B.: 361, Huffman, J.W. : 042, 151, 461 Huggenberg, W.: 403 Hui, R.A.H.F.: 300, 431
Hui, R.C.:,397, 461 Hujama, T. : 425
Hulce, M. : 088 Hung, M.-H.:,413 Hunter, D.H. : 460 Husain, A . i 011, 047, 182 H u s k , G.R. : 093 Hussain, M. : 407 Hussein, F.H.i 2 2 Husson, H.-P. i 33 Hutchins, R.O. : 027 Hvidt, T. : 298 Hwang, C.K.: 184 Hwang, Y.S.: 117 HWU,
J.R.%:,032, 236
Hyatt, J.A. : 273 Hylarides, M.D.: 455 Hyuga, S.: 457 I b e , M.: 4Q4 I c h i h a r a , J. : 098, 141, 189 Ichikawa, M.: 076 Ichinose, H,: 022, 040 Idoux, J.P. : 106, 126 I g a r a s h i , T.: 219
AUTHORS
INDEX
Iguchi, K.: 071 Ihara, M.: 103, 119 Iida, H.: 009, 058, 351, 358 Iida, S.: 068, 184, 250 Iihama, T.: 358 Ikariya, T.: 144 Ikeda, H.: 467 Ikeda, I.: 434 Ikeda, K.: 276, 362, 377 Ikeda, M.: 078, 483, 489 Ikeda, N.: 254, 283, 284, 433 Ikeda, Y.: 254 Ikegami, S.: 297 Ikemi, Y.: 376 Ikemoto, Y.: 342 Imada, Y.: 373 Imai, H.: 356, 435 Imai, T.: 016, 062 Imai, Y.: 044, 099 Imaizumi, M:I 239 Imamoto, T. : 042, 183, 277, 326 331, 342, 348
Imanishi, T.: 337 Imwinkelried, R. : 045, 346, 375 Inaba, S.: 071, 206, 245, 340 Inaba, T.: 351 Inada, A.: 5139 Inamoto, T. * 084 Inanaga, J.": 147, 199, 251 331 9 344, 395
Inokuchi, T,: 237, 299, 440 Inoroata, K. : 138, 142, 488 dInoue, K.: 210, 338 Inoue, N.4 456 Inoue, S. : 105, 336 Inoue, T. : 028 Inoue, Y.: 070, 201, 255 Inouye, M.: 135, 190, 262, 421 Inui, Y.: 203 Ipasli, S.: 006 Iqbal, J.: 402 Iranpor, N. :,053, 056, 21 4 Ireland, R.E. : 305 Iritani, K.i 422 Isagawa,,K. : 044 Ishi, Y. : 311
507
Ishibashi, H.*: 078, 489 Ishida, N.: 033, 205 Ishida, Y.: 729 Ishiguro, M.: 244, 283 Ishiguro, S.: 022, 040 Ishiguro, Y.: 460 Ishihara, K.4 031, 287 Ishihara,,T. : 221, 287 Ishii, Y. : 039, 144, 211, 454 Ishikawa, M.: 310 Ishikura, M.: 127, 375, 388 Ishimto, g.: 065 Ishino, Y. : 344 Ishiyama, T.: 076 Isimura, A.: 219 Ismailov, M.I.: 432 Isobaev, M.D.: 432 Isobe, YI: 422 Isoe, S. : 4ft5, 472 Itabashi, K. : 009, 242 Ito, K.4 036, 038, 130 Ito, S. * 056, 075, 366, 466 Ito, Y.*I 299, 309, 312, 356 380, 435, 478
Itoh, F.4 397 Itoh, K. : 065, 084, 086 252, 308, 418
Itoh, Kao.: 240 Itoh, Kaz.: 240 Itoh, T.: 439 Itsuno, S. : 036, 038, 130 Ives, J.L.: 461 Iwahara, T. : 027 Iwaki, M.: 176 Iwakiri, H.4 432 Iwakuma, T. : 120 Iwasaki, F.: 338 Iwasaki, G.: 235 Iwasaki , H. : 492 Iwasawa, N.: 168 Iwashita,,M. : 31 8, 366 Iwata, C. : 337 Iwaya, K.: 124 Iyer, P.SI: 175, 490 Iyoda, :M: 076 Izawa, T.: 220
508
AUTHCIRS
Izawa, Y.: 248, 456
Izumi, A.: 022, 040 Izumi, T.: 028 Izumi, Y.: 165, 337, 444
475, 482 Jdger, E.4 351 J a b r i , N. : 486 Jacquesy, J.;C.: 315 J a c q u i e r , R. : 363, 376, 378 Jadhav, P.K.: 002, 320, 344 Jagdale, M. : 409 Jagdmann Jr.: E.: 201 Jagdmann Jr.: C.E.: 122 J a g u e l i n , S.: 401 Jain, A.U.: 352 Jakovac, I.J.: 146 James, .B.R. : 215 Jamil, Z.: 054, 210 Janes, J.M.: 447 Janout, V.: 260 Januszkiewicz, K.R. : 081, 082 231 Jaouen, C. : 026 Jasperse, C.P.: 301 Jaworski, K. :*442 J e f f o r d , C.W. : 352 Jellal, A. : 281 , 303 Jensen, K.M. : 168 J i , T.: 330 Jimenez, C.: 110 Jitsukawa, K. 027, 211 Johnson, A.P.i: 366 Johnson, A.T.i 173 Johnson, C.R. : 434 Johnson, R . A . i 325 Johnson, W.S. : 031, 282, 292
435
J o l i d o n , S.4 169 J o l l y , P.W. : 492 Jonczyk, A , : 435 Jones, D.S.4 137 Jones, J.B. : 146, 300 Jones, M.D.: 391 J o s h i , N.N.: 477 J o s h i , P.L.: 166 Jouannetaud, M.-P. : 31 5
Jousseame, B.: 460 Joussen, R.: 302 Juge , S. :,379 Julia, M.*: 064
INDEX
J u l i a , S. : 430 Jung, A.: $40 Jung, M.E. : 301 J w g , S.-H.: 374, 480 Jurczak, J.: 437 Jurss, C.D.: 126 Just, G.: 255 Jutand, A.: 013 Juve Jr.: H.D,: 392 Kabalka, C.W. : 132, 233, 235 432, 453, 455 Kabeta, K.: 261, 341 Kachinsky, J.L.C.: 479 Kadokura, M.: 001, 1 1 4 Kaesler, R.1.: 462 Kagan, H.B. : 024, 177, 220 276, 277, 307 Kageyama, I.*: 144, 21 1 , 448 Kagiya, T. : 120 Kagler, H.: 018 Kahne, D.E.: 084 Kai, Y.: 388 Kaiser, Q.A. : 452 Kaji, A. : 180, 269, 270, 349 4J2, 417, 422, 475 Kajigaeshi, S. : 015, 116, 144 172, 366 Kakihana, M.: 270 Kakimoto, M,:*38? Kakushima, M. i 382 Kallmerten, J . : 294 K m d a , M.: 127, 375, 388 Kamazawa, S. : 065 Kambe, N . : 454 Kaneda, T.: 138 Kamtani, T.: 103, 119 Kameyama, M . i 127, 192 Kamigata, N. : 192, 490 Kamimura, A.: 349, 417 Kamitori, Y.: 028, 065 Kanai, K.: 1 1 4 Kanatani, R.: 027
INDEX
AUTHORS
Kanbara, HI: 439 Kane, V.V. : 230 Kaneda, K . : 027, 211 Kaneko, R.: 124 Kaneko, Y.: 220, 384, 433 Kanemoto, S.: 214, 328, 357 Kang, G.J.: 314 Kang, J.: 256 Kang, M.: 393 Kano, T.: 273 Kantam, M.L.: 054, 210 Kao, L.: 280 Kao, S.C. : 040 Kapnang, H.: 118, 137 Karabelas, K . : 263 Karasawa, A . : 443 Karmarkar, S.N.: 241 Karpf, M.: 473 Kasahara, A.: 236 Kashimura, S.4 104, 217 Kashimura, T. : 156 Katajima, T.: 308 Katayama, E.: 038 Kates, S.A.: 407 Kathawala, F.G.: 217, 322 Kato, J.: 010, 168 Kato, S.: 131, 170, 426 Kato, T.: 438, 455 Katoh, A.: 448 Katoh, T.: 233 Katritzky, B.R.*: 034 Katsuki, T. : 288, 297, 305 312, 313 Katsuro, Y . : 261 Katz, A.H.: 247, 393 Katz, R.B.4 383 Kstz, T.J. : 019 * Katzenellenbogen, J.A. : 191 Kauffmann, TJI : 254, 259, 302 Kawabata, N. : 492 Kawada, K.: 331 , 451 Kawada, M.: 003, 009, 047, 461 Kauada, N. : 044 Kawaguchi, K.: 452 Kawahara, S.: 144 Kawaharasaki, N. : 099
509
Kawai, M. 1 155, 444 Kawai, T.: 2;50 Kawakami, Y. : 072 KawamOto, K . : 077 Kawamura, K.: 395 Kawamura, S.: 364, 367, 398
400, 428
Kawanami, Y.: 288 Kawanishi, Y.: 211 Kawasaki, M.: 315, 343 Kawashima, M. : 41 6 Kay, I.T.: 236 Kaye, P.T.: 452 Kayo, I.: 107
297 .
Kel y eC.E. Keck, ye: 390, 418 Keese, W.:,450 Keinan, E. : 004, 037, 08b
330 440
Kelkar, S.L.: 241 Kell, D.A.: 3x8 Kellogg, R.M. : 260, 323 Kelly, J.W.: 166, 167 Kelly, M.J.4 412 Kelly, T.R. : 130 Kelly, W.J.: 279, 406 Kemmitt, R.D.W.: 391 Kempf, D.J.: 372 Kesseler, KI: 332, 340 Kessler, H. : 017, 018 Kestner, V.M.: 406 Keumi, T. : 203 Kezuka, H.: 007 Khai, B.T.: 022 Khamsi, J.: 167 Khan, M.N.I.: 415 Khan, Md.NII.: 455 Khan, N.H. : 407 Kharitonova, O.V. : 141 Khoshdel, E.: 183 Khoudary, K.P.: 032 K ~ O U Z , B.:
420
Kiaeezadeh, F.: 056, 214 K i j i m a , M.:,248 Kikuchi, H. : 062 Kikuchi, T.: 266, 476
Kikukawa, K.
K i m , B.M.:
INDEX
AUTHQRS
51 0
* : 078
044, 322
Kim, C.-W.: 392, 475 D.: 456 J.-I.: 387 J.D.: 179 J.E.4 179 ~ . g . : 338, 358 S. : 099, 136, 140, 142 152, 200, 218, 321 K i m , S.-C.: 097 K i m , S.S.: 099 K i m , W.J.: 321 K i m , Y.C.4 140 K i m , Y.H. : 104, 176 K i m , Y.J.: 200 Kimura, K.: 341 Kimura, M.: 012 Kimura, T. : 065, 480 Kimura, Y.: 164, 340 King, A.O.4 006 King, F.D.,: 382 King, P.F. : 050, 138 King, S.A.: 42s Kinoshita, H. 138, 142, 488 Kiolle, R.: 379 Kircheyer, S.: 435 Kirihara, T.: 103 K i r k , T.C.4 223 Kirmse, W. : 216 Kirschleger, B.: 168 Kirshenbam, K.S.: 300 Kirszensztejn, P. : 164 Kirtane, J.G.: 175, 178 Kishi, N. : 340 Kishigamj,, Y.: 039 Kita, Y. : 336, 397 Kitagawa, Y.: 292 Kitahara, E.: 283 Kitajima, H.: 203 Kitamura, K . i 144 Kitching, WI : 074 Kiyooka, S. : 307, 324, 452 K jeldsen, G. :,468 Kjonaas, R.A. : 091, 226, 480 Klang, J.A.: 067, 195 Kim, Kim, Kim, Kim, Kim, Kim,
.
Klaver, W.J.: 102 Kleijn, H.: 438 Klingstedt, T.: 157 Klunder, J.M.: 329 Knapp, F.F.: 453 Knapp, S. : 367 Knoch, F.: 140, 353 Knochel, P.: 415 Knouzi, N.: 133 Knudsen, 3.S.: 468 Kejver, A.: 055 KO, J.S.: 200 KO, S.Y.: 328
KO, Y.K.:
142
Kobayashi , H. : 023, 103 Kobayashi, M. : 035, 072, 192 490 Kobayashi, S. : 433 , 462 Kobayashi, T.: 203, 243, 364 * 398, 409, 481 Kobayashi, Y. : 009 Kobori, Y.: 075 Koch, K.: 371 Kochetkov, N.K.*: 218 Kochhar, K.9.: 101 Kochi, J.K. : 176 Kodera, Y.: 124, 141 Koga, K.: 463 Kogure, K.: 062 Kohama, H. : 425 Kohmto,,S.: 352 Kohn, H. : 374 Kohno, S.: 188 Kojima, A&: 272 Kokel, B. :,241 Koketsu, J. : 079 Kokko, B.J.: 132 Kokosi, J.: 063 Kolbasenko, S.I.: 367 Kolhe, J.N.: 352 Kolodziejski, W. : 078 Kolosnitsin, V.S.: 276 Komada, S.: 434 KOmatsu, H.: 489 Komatsu, T. :,391 Kometani, T. : 330
INDEX
AUTHORS
Kominami, K.: 380 Komissarov, V.D. : 276 Konda, N. : 038
Kondo, A.: 190 Kondo, K. : 299 Kondo, T.: 070, 105, 111 201, 255 Konishi, M . i 023, 075, 261 Koreeda, M. 4 143, 336 Kornblum, N. 245, 279, 406
51 1
Kubota, H.:
080, 195 Kudaka, T.: 221 Kudo, K.: 156
Kula, J. : 057
Kulkarni, A.K.: 441, 454 Kulkarni, S.U.: 033 Kulkarni, J.S.: 431 Kulp, S.S. : 231 Kulp, T.: Kumada, ~.'P3D23, 027, 033, 075 Koser, G.F.: 446 205, 261, 341 Kumagawa, T. : 220 Koshiba, M.: 391, 442 Kumar, A.: 058 Koshino, H.: 354 Kumobayashi, H.: 389 Koshino, J.: 063, 290 Kumpf, R.J.: 489 Koskinen, A , : 351 Kunai, A. : 303 Kostantinovic, S. 056 Kunda, S.A.4 132, 455 Kostova, KI: 158 Kosugi , M. : 034, 127, 172, 228 Kunieda,,T. : 321 244, 391, 442, 467 KWZ, H. 4 017, 303 Kuran, W. : 154 Kotake, H.: 138, 42, 488 Kurata, Y.: 102 Kotelko, A , : 094 Kurihara, T. : 482 Kotera. M.: 151 Kurita, M.: 467 Koto, H.: 217, 331 Kurita, Y.: 234 Kotsuki, H. : 420, 091 Kuroda, H.: 307 Kowalski, C . J . : 004, 058, 152 Kuroda, K.: 085 450 Kuroda, T.: 284, 341, 349 Koyama, K.: 460 Kozikowski, A.P. : 069, 292, 370 KurOmaru, H,: 070 Kurosawa, K. : 369 480 KWUSU, Y.: 213 Kozlowski, J . A . : 076, 091, 092 K u s w t o , T.: 183, 342 Kozyrod, R.P,: 406 Kutaleladze,,A.G. : 367 Krafft, M.F. : 214 Kuwajima, I. : 092, 095, 147 Krantz, A. i 364 230, 319, 398 Kraus, G.A. : 152, 362, 453 * 465, 479 Kraue, H.W.: 037 Kuwajima, J. : 282 Krentzien, H.4 446 Kwart, L.D.: 353 Krepski, L.R. : 168 Kwasigroch, C.A.: 284, 373 Kress, J.:,255, 444 Kwast, A.: 435 Kresze, GI : 115 K w a t , E.: 435 K r i e f , A. : 065, 068, 092 Kwiatkowska, C. : 226 095, 166, 182 Kwon, H.B.: 111 193, 230, 258 Kwon, K.S.: 404 Krishnamurthy, S.: 097 Kyler, K.S.: 231 Krolikiewicz, K. : 11 7 Kyung, S.-H.: 025, 041, 406 Kryukova, Yu.1.: 016 Kyz'mina, L.G.: 478 KiikenhUhner, T.: 025
-
,
51 2
AUWORS
Labaudiniere, R. : 1 72 Laborde, E.: 419 Lacher, B.: 181 Lachhein, S.: 016 Ladlow, M.: 414 Ladouceur, G . i 065, 238 Laganis, E.D. : 008 Lai, R.: 446 Laidler, J . K . : 124 Laird, A.A.: 049, 361
Lakshmy, K.V.:
347
Lal, G.S.: 004 am, L.K.P.: 300 Lamatsch, B.: 318
Lamaty, G.: 026 Lambert, C. : 283, 368, 422 Lambert, J.B.: 094 Lambert, P.H.: 130 Lamed, R.: 037, 330
Lammer, 0.: 251 119 Lan, A.J.Y.: Lan, J . Y . : 080 Landgrebe, 152, 453 Landini, D. : 261 Landmann, B.: 024 Lang, R.W.: 417 Lardiccf , L.4 263, 282 Larock, R.C. : 073, 287, 414 415, 439 Larraza, M . I . : 408 Larsen, S.D.4 317, 384 Larson, G.k. : 257, 258 Laszlo, P. : 065, 078, 225, 225 226, 227, 230, 273 357, 431, 487 Lathbury, D.: 379 Lattes, A*: 132, 189 Lau, C.K. : 068 Laugal, J . A . : 487 Laughton, C.A.: 170 Laur, J.: 017 Laurent, A , : 392 Laurent , E. : 448 Laurent, H.: 185 Lautens, M.: 268 Lawesson, S.-0. : 102
K.:
INDEX
Lawrynowicz, W.: 190 Laycock, B.: 074 Lazaridis, N.V.: 355 LaBelle, B.E.: 323 Le Bigot, Y.: 253, 350 Le Goffic, F.: 353 Leach, S.J.: 077, 216 Learn, K.: 027 Leblanc, Y.: 265 Lee, H.S.: 044 Lee, J.I.: 136, 140, 142 152, 218 Lee, K.: 232 Lee, N.H.: 338 Lee, S.D.: 404 Lee, T . D . i 168 Lee, T.V. : 326, 402, 434 Lefker, B.A.: 479 Leftin, M.H.i 250 Lehmkuhl, H. : 268 L e i k a u f , U. : 320 Lemaire, M.: 158 Lennon, P. : 268 Leonard, D.: 145, 162 Leonard, W.R. 473 Leone-Bay, A.i: 229 465 Leong, W.W.H.: Leport, L.: 026 Lerman, 0.: 191 Lespagnol, C.: 247, 370 Lessi, A.: 001 Lesuisse, D. : 31 6 Leszczweski, D.: 306 Levenberg, P.A.: 481 Levkovskaya, G.G. : 01 6 Ley, S . V . : 426 LeGreneur, S.: 115 L i , W.S.: 184 L i c k , C.: 459 Lieberknecht, A. 194 Liebeskind, L.S.i: 090, 163, 293 Liebscher, J.: 244 Lin, J.-M.: 371 Lin, P.: 360 Lin, Y . J . : 414 Lin, Y.L.: 174
INDEX
L i n d e l l , S.D.: 031 Lindig, M. :,303 Lindley, 3 . : 076, i27, 173 Lindsay-Smith, J . R . : 190
LinstrumelJe, G.: 073, 454, 455 Liotta, D. : 164 Liotta, E.L.: $65 Lipshutz, B.H. : 076, 091, 092
361
Lisensky, $.A,: 441 Lissel, M . : 1'67 L i t t l e , R.D.: 401 L i u , H.: 140 L i u , H.-J. : 085 L i u , J . K . : 463 L i u , M.T.H.: 063 Livinghouse, T. : 147, 178, 473 Liz, R.: 205, 390 Lloyd, D.H.: 132 Lociuro, S. : 368 Lock, G.A.: 427 Lok, K.P.: 146 Long-Mei, Z . : 301 Lopez, C.: 054, 209 Lorenz, K . T ? . ~ 094 Loudon, G.M. i 116 Lounasmaa, M. : 351 Lovich, S.F.: 280 Liining, U.: 160 Lu, L.D.L.: 325 Lu, S.-B.: 266 Lucchetti, J,: 357, 431, 487 Luche, J.-L. : 060, 089, 107 Luehr, G.W.: 180 Luengo, J.I.: 336 Luk'yanets, E.A.: 094 Luke, R.W.A.: 366 L m a , P.K.: 380 Lwt, S.R.: 466 LuO,
51 3
AUTHORS
F.-T.:'206,280, 484
Lupo Jr.: A.T.: 371 Lusinchi, $.: 031, 123, Lutz, R.P. : 492 Lygo, B.: 426 Lyon, J.T. :,173 Lysenko, Z. : 354
259
P i a r k l , R.:
170
Mabury, S.A.: Macdonald, T. Lli'a 478 Machida, H.: 411 Mack, J.F.: 34p Macomber, D.W. : 473 MacFerrin, K.D. : 326 MacMillan, J.: 196 Maddaluno, J.: 459 Madyastha, K.M. : 1 20 Maeda, K.: 337 Maeda, N.: 318 Maekawa, E.: 399 Maekawa, T.: 287 Mafunda, B.G.: 073 Magnin, D.R. : 229 Magriotis, P.A.: 209 Mai, K. : 242, 385, 386 Maienfisch,,P. : 403
Maier, W.F. : 198
Maigrot, N.: 234 tlaione, A.M.: 024 Majchrzak, M4W. : 094 Majetich, G. : 087, 422 Mak, K.T.: 380, 387 Makabe, Y. :,360 Makosza, M. : 435 Malfroot, T.: 121 Malmberg, H.: 127 Mamada, A.: 246 Manabe, H.: 122, 135 Mandai, T.: Q03, 009, 461 Mandal, A.K. : 142 Mander, L.N.: 402 Mane, R.: 409 Manescalchi, F.: 028, 183, 463 Mangeney, P. : 089 Mangoni, L.: 157 Manitto,,P.: 233 M a , G. : 108
Manna, S.: 185, 349 Manoharan, T.S.: 120 Mansuy, D . : Mantanari, F:!' 010 Marais, D.: 353 Marcano, M.M. : 491
514
AUTHORS
Marchand-Brynpt , J. : 1 01 Marchelli, R4 : 449 Marchese, G. 089, 206, 209 Marcos, M.: 3i8 Marcuzzi, F.: 002 Maresca, L.: 276 Harherbe , R. :,154 Mariano, P.S. : 119, 390 Marinelli, Fa: 348 Marino, J.P. : 399, 419 Marquet, J. : 462 Marra, J.M.: 134 Marrero, R.:,392 Marsi, M.: 441 , 470 Martelli, G.: 028, 109 Martin, A.: 230 Martin, J . C . : 382 Martin, M.G.: 259 Martin, O.R.: 298 Martin, S.J.: 286 Martinez Alvarez, R.: 080, 456 Martinez-GalJo, J.M. : 448 Martinez, J. : 017 Martz, J . T . i 121 Maruoka, K. : 038, 039, 064, 096 122, 128, 129, 192
-
326, 339, 485 318, 343, 396 489 Masamune, S.*: 010, 044, 150 322, 350 Mason, R.: 257 Massardo, P.: 485 Masset, P.: 3#9 Mastalerz, H. : 018 Masters, N.F.: 077, 2 6 Mastorilli, E.: 447 Masuda, M.: 410 Masuda, R. : 028, 065, 080 Masuda, T.: 398 Masuda, Y.: 139, 246, 289 Masunga, T. : 465 Masuyba, A.4 434 Masuyama, Y. : 210, 213 Mather, A.N.: 030 Mathy, A . : 078, 226 Maruyama, K.:
INDEX
Matsubara, S.: 012, 159, 334
345, 347, 357
Matsuda, A.: 398 Matsuda, H.4 344 Matsuda, I. : 337, 475, 482 Matsuda, T.: 078 Matsumiya, K.: 229 Matsumto, H.i 071 Matsumoto, K. : 075, 376, 383
*
396 023, 252, 308 466 Matsumoto, T.: 038, 128, 183 336 Matsumura, N.*: 302 Matsumura, Y.: 103, 129, 217 118 -Matsuo, T.: 189 Matsuoka, H.: Hatsushita, H.519022, 040, 072 Matsuura, T.: *305, 356, 397 Matteso, D.S. i 045 Matteson, D.S. : 175, 346 Maumy, M.: 195, 208, 466 Maus, S.: 024 Mazur, D . J . : 444 McBride, B.J.; 173 McCarthy, K.E.: 091 McClure, C.K. : 444 McCollum, G.W.: 132 McCoy, R.K.: 359 Matsumoto, M.
:
McDermtt, S.D.: 112 McGarry, D.G.: 100 McGee, M.J.: 231 McGuire, M.A.: 365 McKean, D.R. : 436 McKeer, L.C.: 190 McKenna, J.: 241 McKervey, M.4. : 228, 429, 464 McKillop, A. : 247, 274, 275
393
McMaster, D. :*OO6McMurry, 3.E. : 223, 267 McNab, H. :,382 McNelis, E. :,403 Mechoulam, R. : 427
INDEX
AUT'HOFS
Mehrota, 4.K.: 011, 182 Mehta, G. : 449 Mehta, P.G.: 347 Meier, G.P.: 382 Meier, M.: 247 Mei j e r , J. : 438 Meist.er, A.: 304 Melany, M.L.i 427 Mellor, J.M. : 110, 278 Meltz, C . N . : 179 Mendoza, L. : 121 Menichi, G.: 241 Menoret, G.: 220 Mera, A.E.: 489 Merrifield, J.H. : 472 Mert.ens, A,: 435 Metra, P.: 078 Metzger, J.i 446 Meunier, B. * 177 Meyer, G.: 2iO Meyers, A.I. : 063, 119, 122
Minami, I.: 117, 212, 405
515
417, 421, 466 472, 474, 478 479, 480, 483 t191 Mincione, E. : 159 Minobe, M. : 404, 345 Mioskowski, C. : 185, 436, 439 Miranda, E.I.: 066 Mirskova, A.N.: 016 Misawa, H.: 290, 360 Mishra, P.: 138 Misintsev, V.V. : 464 Misiti, D.: 237, 275 Mison, P.! 392 Misu, D.: 215, 221, 289 Mita, T.: Q84, 342 Mitani, M. i 460 Mitsudo, T. : 001, 290, 423 M i t s u i , H.: 274 Mittal, R$.: 274 134, 321, 404, 479 Miura, M. : 222 Michael, J . P . : 383 Miwa, T.: 334 Michelotti, E.L.: 068, 071, 250 Miyake, H. : 433, 484 Miginiac, L. 420, 442 Miyake, J.: Miyasaka, T.'T9218 Miginiac, e.*I 381, 488 Miyashita, M.: 303 Migita, T. : 034, 127, 172 Miyaura, N.: 076, 176, 490 199, 228, 244 Miyazaki, M.: 084 391, 442, 467 Miyazaki, T.: 129 Mihailovic, M.k.*: 056 Miyazaki, Y.: 345 Mihelich, E.D. : 467 Miyazawa, S.: 377 Mikaelian, G.S.: 478 Miyoshi, N . : 010 Mikami, K.: 029, 249, 340 Mizuguchi,,Y.: 203 Milenkov, B.: 409 Mizuno, K. : 483 Milesi, L.: 261 Mizusaki, S.: 022, 040 Miller, D.D.: 223 Mizuta, Y.: 212 Miller, J . A . : 206, 289, 468 Mizutani, M.: 400 474, 488 Mobbs, B.E.: 170 Miller, R.D.*- 436 Moberg, C.: 422 Miller, R.O.*: 439 Modena, G.: 276, 492 Mills, S.: 11; Moghaddam, M.E.: 213 Milstein, D. : 023, 082 Mohajer, D.:,213, 214 Mimun, H.: 177 Mohamadi, F. : 151, 265, 309 Mohan, R. : 407 Mohler, D.L.: 427
51 6
INDEX
AUTHORS
Moison, H.: 09Q Molander, G.A. : 041, 073, 076 224, 283, 322
*
323, 339, 470
Molina, P. : 034, 149 Molinari, H.: 436 Molinski , T.F. : 329 M O ~ O K ~ ~ O VA.N.: ,
464
Morisaki, Y.: 003 Morita, T.: 203 Morita, Y.: 086 Morizawa, Y.: 204, 250, 269
334, 345, 405 061 21 3 081 294 029, 046, 049 179 Morton, J . A . : 381 Mortreux, A , : 254 Moskal, J. : .061, 471
Pforizur, J.-p.: Moro-Oka, Y. : Morrissey, MIM.: Morrow, C . J . Morton, H.E.*I
Momosi, D. : 071 Monaco, P.: 157 Monkiewicz, J. : 477 Monkovic, I.: 123 Monobe, H.: 218 Montanari, F.: 311 Montanucci , M. : 171 Mostaf'avipoor, ZI: 211 Monte, W.T.: 401 Motherwell, W.B. : 115, 129, 181 Monteil, T.: 351 194, 234, 385 Motherwell, WIJ. : 460 Montes, J . R . : 379 Montevecck$, P.C. : 380 Motohashi, S. : 338, 409, 428 Monti, D. :,233 Mourad, M.S.: 233 Moody, C . J . : 154 Mouzin, C. : 426 Mook Jr.: R.: 162 Moya-Portdguez , M. : 1 01 Moore, D.W.: 346 MUler-Starke, H.: 245 Moore, J.L.: 396 MUler, P.: 052, 275 Moore, L.L.: 317 Miinsterer , H. : Moracci, F.M. 365 Muchowski, J .V. 5~67 Morales, H.R.i: 121 Mukaiyarna, T. : 010, 047, 048 Morand, P.: 056 088, 141, 168 Mordini, A . : 229 201, 320, 345 Morella, A.M.: 401, 447 407, 416, 431 Morellet, C.: 312 432, 433, 461 Moreno-Manas, M. : 462, 485, 4.91 467 Morera, E. : 202 Mukerji, I.: 032 Moret, E.: 348 Mullican, V.D.: 395 Moretti, R . : 297 Mulzer, J. : g51 Mori, A , : 038, 096, 287 Murahashi, S. : 124, 274, 360
'1
326, 454
Mori, I.: 343, 358 Mori, K.i 277, 316 Mori, M. : 107 Mori, S.: 126, 156 Mori, T.: 020, 051, 207, 321 Mori, Y.: 411 Moriarty, R.g. : 238, 333, 335 Morimoto, T. : 126, 211, 353 Morisaki, K.: 013, 070
Murahashi,
*
s.-I.'~~Ios, 247, 355 389
Murai, S. : 058, 077, 092, 097
170, 235, 259, 426 426, 428, 458 Murai, T. : 131, 170, 426 Murakami, M.: 047, 048, 416 462 Murakami, T.: 211
*
INDEX
AUTHqRS
Murakami, Y.*: 075 Murata, T.: 445 Murayama, 8.: 219, 266, 476 Murota, K. : 398 Murray, S.: 065, 238 Muruoka, K.: 129 Muruyama, 5 . : 075, 391 Muzart, J. : 216, 374, 423, 481 Myles, D.C.:,326 NBsw, J.H. : 366 Naderi, M.: 054 Naef , R.: 091 , 296 N a f t i , A . : 392
Nagao, Y.: 212, 359 Nagaoka, H.: 048 Nagasaki, N.: 015 Nagashima, E.: 310 Nagashima, H.: 078, 232 Nagasuna, K.: 232 Nagata, R.: 305, 397 Nagata, SI: 107, 157, 418 Nagel, U. : 084 Nagusa, H.: 104 Naim, S.S.: 407 Najera, C.: 110, 308, 370, 448 Naka, K.: 394 Nakagawa, I.: 327 Nakagawa, T.: 015, 116, 144
366
Nakagawa, Y.: 290 Nakahama, S.: 036, 038 Nakahara, Y.: 184 Nakai, K.: 113 Nakai, S.4 064, 192 Nakai, T. : 029, 283, 340 Nakajima, N.: 247 Nakajima, T.4 009, 309 Nakamura, A.*: 232, 337 Nakamura, E. : 147, 230, 319
398, 465
Nakamura, H.: 243 Nakamura, K. : 1 98 Nakamura, N.: 129 Nakamura, T.: 408 Nakanishi, A.: 160 Nakano, M.: 038, 127
51 7
Nakano, T.: 039, 311 Nakao, K.: 014 Nakashi t a , ,Y. : 458 Nakata, T. : 042, 043, 307 Nakatani, H.: 078 Nakatani, K.: 472 Nakatani , M. : 304, 369 Nakatani, Y.: 287 Nakatsuka, T.: 412 Nakatsukasa,,S.: 284, 328, 417 Nakayama,*J. : 411 Nambu, Y. : Namy, J.L.:
248 024, 220, 307 Nanbu, H.: 345 Naota, T.: 109, 247, 389 Napolitano, E. : 447 Narang, S.C.4 047, 192, 246 Narasaka, K. : 309, 310, 315 3 9 , 334, 345 Narasimhan, N.S. : 042, 128 Narayana, C. : 232 Narayanan, K.: 073, 414 Naritomi , M. : 078 Narula, C.K.: 380, 387 Naruse, X.: 433 Naso, P. : 089 Natalie Jr.: K.J.: 478 Natarajan, S.: 471 Natile, C.: 275, 276 Natsugari, H.: 375' Nazasaki, N.: 144 Nazer, B. : 051 Ndebeka, C.4 462 Negishi, E. : 006, 072, 206, 206 280, 407, 441, 468 474, 484, 488 Negishi, Y.: 244
Negoro, K.: 052 Nemo, T.E.i 177 Nmoto, H. : 232 Neubert, M.E.: 014 Neunann, B . i 167 Nemann, 8. : 011 New, J.S. : 131 Newington, I.M.: 097, 352 Newton, T.W.: 438
518
Nguyen, S.L.: 991 Nicholas, K.MZ : 280 Nichols, D,E. Nickon, A. : Nicolaou, K.C?
*
132
Niessner, M. : 285
184
Nikam, S.S.: 481 Nikishin, C . I . : 464 N i k i t i n , Yu.E.: 276 N i k u l i n , A.Y.: 367 Nilsson, M. : 127 Nimmesgern, H. : 103
Nisar, M.: 228, 479 Nishi, S.: 477 Nishida, T.: Nishiguchi, I?? 057, 467 Nishihara, H.: 211 Nishimoto, S.: 120 Nishina, H.i 240 Nishino, H. :,369 Nishiyama, H. 252, 308, 481 Nishiyama, K.*I 125, 240 Nishizawa, M.: 037 Nitta, K.: 458 N i w a , H.: 216 Noels, A.F.: 093 Noguchi, S.: 218 Nohira, H.i 026 Nokami, J. : 235, 344 Nornoto, T.: 248 Nomura, M . i 222 Nonaka, T. : 143, 328 Nordberg, R.E.: 415, 416 Norisue, Y.: Normant, J.-F!'i) 073, 089, 173 208, 220, 389 415, 454, 455
-
486 Nowak, M.Al.: 208, 304 Noyori , R. : 037 Nozaki, H.:
INDEX
AUTHORS
066, 208, 263, 324,
097, 159, 204 214, 250, 251 266, 269, 284
334, 341 8 343 345, 347, 349, 358 405, 417, 422, 476
Nozaki, Y.:
-
141 Nudelman, A. 440 Nugent, W.A.*: 487 Nunmoto, S.*I 072 Nutaitis, C.F.: 021, 327 Nystrm, J.E.: 125 O'CoMor, B.: O ' D O M e l l , M.J?; 297
O'Malley, G.J.: 397 O'Reilly, N.J.: 330 Obayashi, M.: 342, 425 Obrecht, R.: 242 Obrzut, M.L.: 161 Obushak, N.D.: 400 Ochi, M.: 020 Ochiai, H.: 207, 220, 364 398, 408, 471 Ochiai, M.: 212, 267, 357, 359 Oda, D.: 270, 388 Oda, H.: 204, 269 Oda, 1.i 388 Oda, M. : 076 Ogata, M.: 199 Ogata, T.: 172 Ogawa, A,: 259, 458 Ogawa, H.i 300, 391 Ogawa, M. : 039, 211, 311 Ogawa, S.: 236, 327 Ogawa, T.: 190 Ogawa, Y. : 048 Ogibin, YIN-: 464 Ogura, F.*: 135 Ogura, K . : 009, 351, 358 Ohannesian, L.: 226, 449 Ohashi,.Y.: 117, 223, 418, 474 Ohhara, H.: 253 Ohhashi, K. : 034 Ohira, N.: 135 Ohishi, M. : 336 Ohki, H.: 345 Ohmura, M.: 488 Ohno, A . i 198 Ohno, M. :,277, 316 Ohsawa, T. : 119, 203 Ohshim, M.4 010, 047, 048, 416 Ohshiro, Y. : 188, 465
INDEX
AUTHORS
51 9
180, 269, 270, 349 412, 417, 475 Oohashi , M. : 124 Ookawa, A.: 845, 090 Oppolzer, W. : 089, 090, 297 372, 412, 413, 492 Orena, M.: 314, 332 307 Oriyama, T.: 201, 320, 345 Ortar, G. : 202 Ojima, I. : 1 1 1 Ortuno, R.M.: 491 Oka, S.: 043, 198 3saka, N.: 481 Okada, H.: 482 Osakada, K.: 144 Okada, M.: $77 Osawa, T.: 106 Okahara, M. 434 O s b r n , J.A.: 255, 444 Okamoto, T.*I 043 Osby, J.O.: 234 Okamoto, Y . : 261 Oshikawa, '6. : 184 Okano, K.4 113, 353 Oshirna, K. : 097, 204, 208 Okano, M. : 181 214, 250, 251 Okawara, M.: 144, 211, 272 263, 266, 269 345, 448 284, 324, 328 Okawara, R . : 344 334, 343, 345 Okazaki, M.E.: 138, 382 347, 349, 357 O k a z a k i , R. : 104, 122, 386 358, 405, 417 Okame, T.: 347, 476 Oshino, H.: 147, 398 Okinaga, N.: 1 1 1 Ostarek, R.: 024 O k i t a , M.: 107 O k i t a , M.: 363 Osugi, J.4 383 Osuka, A. : 080, 167, 189, 195 OkonkwoJ, J.O.: 402 201, 204, 243, 270 Oku, A. : 032, 093, 271, 327 333, 411, 481 341, 443 Oswell, K.D.: 124 Okuda, Y.: 097, 208, 250 Otani, S.4 376, 383 251, 417 Otera, J. : 003, 009, 047, 066 Okukado, N.: 280 327, 360, 461 Okumoto, H.: 151 Otsubo, K . : 147 Okumura, HI: 129 Olah, G.A. : 01 1 , 047, 108, 175 Otsubo, T.4 135 182, 189, 191, 192 O t s u j i , Y. : 044, 483 226, 244, 246, 302 O t s u k a , H . 4 076 Otsuka, S. : 389 435, 449 O t t , W.: 164 Olano, B.: 385 Ottana, R.: 002 Olofson, R.A, : 121, 187 Omori, K.: 284 Ou, K.: 133 Ousset, J.B.:,436, 439 Omura, H. 235 Overrnan, L.E. : 106, 131, 138 Onaka, M.i: 165 316, 382, 388 Onishi, 360 44'3. _ . 492 Onka, M. : 444 Owa, M.: 038
O h s u m i , T.: 105, 135, 467 Ohta, H.: 141 Ohta, M.: 334 Ohta, T.: 101, 135, 388 Ohtani, B.: 12C Ohtsuka, H.: 043 Oikawa, HI: 098 Oishi, T.*: 042, 043, 203,
0
x.:
Ono, N.*:
520
INDEX
AUTHORS
Oyamada, H. : 036, 037, 318 OzaKi’, J.: 490 Pac, C . : 128 Padmanabhp, S.: 280 Padwa, A. : iO3, 270 Page, P.C.B. : 408, 451 Paget, W.E.: A91 Pagnoni, U.M. : 452 Pai, F.-C.: 310 Pai, G.G.: 320, 329 Paisley, 2.D.: 070 Pak, C.S. : 086 Paknikar, S.K.: 175, 178 Palla, F.: 282 Palmieri, G.: 237, 275, 276 Palmino, E . i 291, 350 Palomo, A.k. : 099 Palomo, C . : 054, 185, 187
* 209, 240, 448 Panunzi, A. i 343 Panunzio, M. : 028, 109, 183 Papadopulos , K. :,353, 402 Papaleo, S.: 229 Papini, A.: 313
Paquette, L.A. : 320 Pardo, S.N.: 414 Park, K.B.: 022 Park, W . S . : 319 Parker, D.A.: 091 Parkhurst , C .S. : 437 Passarotti ,,C. : 085 Pasto, D . J . : 271 Pastorelli, S.: 229 Patel, D .D. :,226 Paterson, : 175 Pathak, T. : 055 P a t i l , G.: 242, 385, 386 P a t i l , P.A.: 042 Patricia, J.J,: 074 Patrick, T.B. : 400 Patrie, W . J . : 143 Patt, H.: 153, Pattenden, G. : 212, 414, 444 Paudler, W.W.: 210 Pauluth, D.: 055 Pauly, M.: 247, 370
&.
Pavlov, S.: 059 Pazynina, G.V.i 094 Pearlman, B.A. : 267 Pearson,.A.J.*: 402, 415, 455
*
470, 475
Pearson, W.H. : 124, 392 Pearson, W.W. : 098 Pedrosa, R.: 297 Peevey , R .M. :,374 Pellacani,,L. : 368 Pelter, A. : 033, 114, 264, 308 Pena, M.R.: 419 Pennetreau, P.: 065, 230, 273 Peretz, M.: 004 Perez- Juarez ,,M. : 1 21 Periasamy, M. : 232 Perichon, J.: 013, 026, 222
260
Perie, J.J.: 132 Perni, R.B.: 241 Perrone, E.: 018, 185 Perry, D.A.: 21g, 444 Perry, M.W.D.: 234, 352 Perry, R . J . : 469 Perumal, P,T. : 044, 344 Pete, J.P. : 198, 374, 423, 459 Peter, R.: 024, 025 Peters, E.-M.: 146 Peters, K.: 146 Petersen, J.S.: 044, 350 Peterson, J.R.: 161, 162, 393
419, 446
Peterson,,R.T. : 394 P e t i t , F. : 254 P e t i t , M.: 254 Petraglia, S.P.: 075 Petragnani, N.: 005, 286 P e t r i e r , C.: 089 Petrignanil, J.-F.: 226, 446 Pews, R.G. : 354 Peyton, K.B.:,450 Pfenniger, A.*: 329 P f i s t e r , J . R . : 113 Pfluger, F.: 013 Phillips, B.T.: 380 Piccardi, P,: 485
INDEX
AUTHORS
Piccolo, o.*: 313 Pichon, C2: 167 Piers, E. : 250 Pietre, S.: 068 Pietrusiewicz, K.M. : 477 Pigiere, C.L.: 376 Pigiere, Ch.: 363, 378 P i k e , d . : 988 Pindur, U. : 356
,
Pinhas, A . R . i 291 Pinkey, J.T. i 406 P i n n i c k , H.W. : 101 Pinsker, O.A.: 197 Pinto, A.C;: 399 Piotrowski, A&: 264 Pirrung, M.C. : 434 Pitchen, P.: 276 Piteau, M.: 121 Piva, 0.: 423 P l a u t , H.: 045 Plenat, F.: 376 Plessi, L.: 028, 183, 463 Pltlmer, R; : 186
Pluscec, J.: 471 Pogorzelska-Marciniak, B. : 154 Poirier, J.-M.: 451, 459 P o l i , C.: 090, 310 Polishchuk, O.P. : 400 Poll, T. :,306 Polla, E. : 109, 225, 227 P o l l i n i , C.P.: 471, 483' Polywka, M.E.C.: 171 Pong, R.Y.: 096 Ponomarev, A.B.: 001, 221 Poon, Y.-F.: 392, 400 Pornet, J.: 420, 442 Portella, C . i 198 Porter, N.A. : 229 Porzi, C.: 322 Posner, C.H. : 021, 088, 170 266, 428 Poss, M.A. : 360 Potenza, J.C.: 350 Potnis, S.M.: 461 Poupart, M.A.i 063 Pradhan, S.K. : 043
521
Prager, B. : 322 Prahash, I.: 333 Prajapati, D.: 385 Prakasa Rao, A.S.C.: 173 Prakash, C.K.S.: 226, 449 Prakash, 0.: 238, 335 Prandi, J.: 177, 220 Prasad, G.: 291, 350, 478 Prasad, J.J.N.V.: 317 Prasad, K. : 322 Prat, M.: 491 Pratt, D.V.: 363
Previtera,
k.:
157
Pri-Bar, I. : 202, 248 Price. M.F.: 469 Price, T.: 08 Procter, C. 030 20 Pugin, B.: Purr i n g t on, S.T.*: 355, 429 P u t t , S.R.: 267 Quabeck, u. 266 Quader, A , : 077 Quadri, M.L.: 261 Qudllich, C.: 430 Q u i l l e n , S.L.: 119 Quinn, N.K.: 075 Quintard, J.-Psc: 384, 460 Rabinovitz, M. : 261 Radhakrishna, A.S.: 115, 116 Rafizadeh, K.: 168 Ragnarsson, U. : 138 Rahamim, ,Y. : 082 Rahn, A. : 040 Rahn, B.J.: 073 Ra jagopalan, S. : 457 Raju, N.: 169 Rakiewicz, D.M.: 306 Ram, S.: 135, 378 Ramachandran, J.: 017 Ramadas, S.R.: 017 R a ma n , K.: 403 Ramani , B. : 085 Rambaud, M. : 168, 420 Rampi, R.C.: 126 Rand, C.L.: 072 Randriamahefa, S.: 012
522
AUTHORS
*
INDEX
Ricard, M,: 096 Rao, A.S. : 166, 175, 178 Ricci, A. : 229, 313, 315, 336 Rao, C.G.: 115 Ricci, M.: 176 Rao, C.T.: 031, 456 Rice, E.M.: 075 Rao, H.S.P.: 449 Richards, I.C.: 402 Rao, V.B.: 219 Richardson, K.A.: 326, 434 Rappa, A.: 032,,487 Richardson, S.: 360 Rasmussen, J . K . : 168 Richey Jr.: H.C. : 083 Ratananukul ,,P : 464 Rathke, M.W. : 208, 304 Rico, I.: 189 Rathore, R . : 160, 21 3, 238 R i d e l l a , J . i 224 Ratovelomanana, V.: 073, 454 Rieke, R.D. : 071, 206, 245 455 340 Raucher, S. : 137, Rieker, W.F.: 122 Riepel, G.: 036 Rautenstrauch, V. : 469 Rieu, J.-P.i 426 Ravenscroft, P.D.: 219 Rigby, JIH. : 046 Ram-Petersen, L.S.: 468 Rim, B. : 247, 370 Ray, T.: 470, 475 Riguera, R.*: 368 Razintsky, M.: 292 Rimpler, M. : 450 Reagan, J.: 026 Ringer, E.: 020 Rebrovic, L.: 446 Riondel, A.: 462 Reddy, D.B.: 093 R i s t , G. : 154 Reddy, N.P.: 054, 210 Rivera, A,D.: 396 Reed, J . N . :,361 Reetz, M.T. : 024, 025, 041, 079 Rasch, L. i 086 209, 227, 245, 329 Robert, A. : 401 332, 340, 404, 406 Roberts, J X . : 010 Robinson, B.L.: 447 474 Regen, S.L. : 164 Robinson, P.L.: 166 Rocherla, U.S. : 283, 288 Regenye, R. : 325 Roder, H.: 146 Regondi , V. : 171 Rodriguez, A.D.: 440 Reibenspies, J.: 298 Rodriguez, M.A.: 457 ReibenspiesZ J.H.: 310 Rodriques, K.E.: 367 Reich, H . J . : 301 Roggo, S.: 025 Reimer, C.J.: 061 Rokach, J.: 165, 382 Reinking, P.: 165 R o k i c k i , G.: 154 Reissig, H.-U. : 152 Rolmdo, C.: 064 Remuson, R.: 363 Rolla, F.: 261 Renaud, J.-P,: 177 Rollin, Y1: 260 Renaud, R.N. : 383 Romeo, A. : 054 Rendenbach,,B.E.M.: 353 Romeo, G.: 002 Renga, J.M. : 165, 301 Ronald, R.C.: 254 Repic, 0. : 322 Rondrianielina, B. : 442 Restelli, A.: 311 Ronzini, L.: 989, 206, 209 Reuman, M.: 063 Rosenblum, M. : 108, 268, 470 Rhee, I.: 235 Rosenthal, S.: 408, 451 Rheingold, A.L. : 387
.
*
*
INDEX
523
AUTHORS
Roskamp, E.J.: 434 ROSS, B.A.: 116 Rosser, R. : 308 Rosser, R*M.: 114 Rossi, R. : 001, 281 Rossini, G.: 336 Roth, Z.: 440 Rouessac, F.P.: 299 Rousseau, g. : 094, 420 Roussi, G. : 118 Royer, J.4 133 Rozen, S. : 178, 191, 450, 452 Rlichardt, C. :,247 Rubottm, G.M. : 392 Rudham, R.: 212 R u d i s i l l , D. : 01 4 Ruggeri, R.: 444 Russell, C.E. : 468 Russell, D.N.: 228 Russell, J.J.: 212, 444 Ruzziconi, R.: 394 Ryabov, V.D.: 067 Ryang, M.: 235 Rychnovsky, S.D.: 162 R y u , I.: 097, 092, 235, 458 Sabadie, J.: 020 Sabirov, S.S.: 432 Sablukova, I.: 037 Sabol, M.R4: 405 Saburi , M. : 144 Sadhu, K . M . i 175 Saednya, A. 242 Saegusa, T.*i 356, 380, 435 1
477
Saeki, S.: 235 Sahai, M.: 440 Sahlberg,,C.: 077 Saigo, K. : 236 Saindone , M. : 1 64 S a i t o , E . i 109 Saito, I. : 305, 397 S a i t o , M.: 240 S a i t o , Y.: 343 Saitgh, T.: 203 Sakaguchi* H. : 252 Sakai, K . : 460
Sakai, S.: 153, 160, 473 Sakaitani , M. : 076 Sakakibara, Y.: 303 Sakakura, T.: 230, 378 Sakane, S.: 128, 129, 485 Sakane, T.: 131 Sakata, K.: 220, 384 Sakata, Y.: 377 Sakdarat, S,: 046 Sakurai , H. : 044, 064, 237 377, 430, 443 453, 472 Sakurai, K.: 039 Sakurai , M. : 039, 064 Sakurai, Y.: 286 Sakuta, 481 Sala, R. : 085 Salama, P . i 172 Salaun, J. : 253 Salazar, J.A.: 182 Saleh, S.A. :,346 S a l l a d i e , G. : l?tr S a l o ~ M.F./ , 414 Saloman, R.G. : 414, 479 Salunkhe, M.: 409 Samayaji, V . i 453 Sammes, P.G. : 121 Sampson, P.: g24 Sanchez, I.H. : 408 Sanda, F.: Sandhu, J.S.2g? 385 Sandison, M , : 291 , 350 Sandler, J.: 254 Sa ndri , 314, 332 Sano, H. : 034, 122. 172 192, 199, 244 345,,391, 442 Santaniello,,E. : 060 S a n t e l l i , M. : 281, 303 S a p r i t o , A.: 343 Sardarian, A.R.: 054 S a m , D.N.: 154, 198, 252 Sarma, J.C.: 154, 252, 425 Sas, W.: 278 Sasaki , K. : 266, 303, 430 Sasaki , M. :. 467
4.:
9.:
524
Sasaki, T.: 277, 316 Sasakura, K.: 335 Sasatani, S.: 129 Sassaki, K,: 064, 237 Sasson, Y. : 011, 035, 292 Sastry, K.A.R.: 453 Sastry, V.V.S.K. : 017 Satish, #.V.: 461 Sato, F. : 248, 439 Sato, K.: 044, 151 Sato, M.: 097, 204, 248, 266 Sato, N.4 195 Sato, R. : 240 Sato, S . i 337, 475 Sato, T. : 008, 020, 044, 051
068, 184, 207, 219 234, 250, 266, 322 341, 425, 441, 476 * Sato, Y . : 127, 239 Satoh, J.Y.: 302 Satoh, T.: 220, 237, 338 384, 409 Satoh, Y.: 354 Satomi, M. : 428 Satyamurthy, N.: 193 Sauerwald, M.: 209 Savoca, A.C.: 034 Savoia, D . : 319 Sawahata, M. : 342 Sawaki, Y.: 012 Sawamura, M. :,299, 380 Sawicki, R.A. : 155 Sawyer, J.S.: 478 Sayo, N. : 283 Scallen, T.J.: 294 Scanga, S.A.: 333 Scanlan, T.$.: 445 S c e t t r i , A. 4 252 Schaap, A.P. : 291, 350 Schamp, N . 4 130, 318, 381 Schank, K. : 459 Schauder, J . R . : 258 Scheibye, S.: 102 Scheigetz, J.: 068 S c h i a v e l l i , M.D.: 427 Schiess, M.,3?2, 383
INDEX
AUTHORS S c h i l l e r , A . 4 186 Schinzer, D. : 088, Schlessinger,,R.H. : 360 Schlosser, M. : 348 Schmid, J.: 170 Schmidt, S.4 167 Schmidt, U . : 194 Schmidtberger& S.: 332 Schneider, F.*: 339 Schneider, M. : 300
Schnur, J.M. : $81 Schtillkopf, U. : 377 Schobert, R.: 222
Scholl, B.: 169 Scholler, 198, 459 Scholz, D. : 274, 271, 429 Schreiber, S.L. : 026 Schroeder, J.E.: 032 Schultz, F.W.: 346 Schultze, L.M.4 365 Schuster, C.B. : 080 Schwartz, E.4 444 Schwartz, J. : 254, 437 Schwellnus, K . 4 404 ScolasticQ, C . : 310 S c o t t , F. : 073 S c o t t , W.J.,262, 419 Scripko, J.: 370 Seamon, D.WI: 427 Seebach, D. : 025, 045, 296
8.:
308, 312, 318 335, 346, 375, 383 Segoe, K.: 435 S e i t z , S,P.: 048 Seki, Y. 077 Sekiya, M:*: 113, 126, 276, 310 ,353,362, 377 Seko, T.: 399 S e l f , C.R.: 469 Selikson, S.J.: 231 Selim, A.: 150 Selle, B.$.: 446 Selve, C . : 133 Sernenovskii, A.VI : 197 Semmelhack, M.F. : 053, 413, 437 463, 482
-
INDEX
AUTHORS
Senaratne, K#P.A.: 357 Senet, J.-PA : 121, 136 Sennyey, G. : 136 S e r a g l i a , R.: 276 Serebrenni kova, G. A. : 052 S e t , L.: 231 Seth, K.K.: 037, 330 S e t h i , S.P.: 402 Seto, K.: 410 S e t z e r , A.: 451 Seyferth, D. : 397, 461 Shabarov, Yu.S.: 141 Shadday, J . : 165 Shafikov, N.Ya.: 276 Shahriari-Zavareh, H.: 037 Shanklin, P . L # : 424 Shanmugam, P. : 012 Shapiro, M.J,: 322 Sharma, R.P. : 047, 154, 179 198, 252, 425 Sharp, M.J.: 102 Sharpless, K.B. : 293, 297, 300 312, 314, 316 325, 328 478
Shashkov, A.S.: Shea, K . J . : 410 Shea, R.G.: 295, 372, 374 Sheets, R.M.: 210 Sheffy, F.K.: 074 Shellhamer, D. F. : 447 Shen, Y.: 055, 419, 423 Shen, Y.C.: 040 Sher, P.M.: 436 Shereshovets, V.V. : 276 Sheth, J.P.: 093, 347 S h i , L.: 359, 380 Shibasaki, K. 009 Shibasaki, M.': 048 Shih, J.: 302 Shih, J . G . : 189, 191 Shim, S . C . : 145, 196 Shima, K.: 128 Shimada, J.: 465 Shimasaki, Y.: 307 Shimizu, H.: 270, 411, 455
525
Shimizu, I.: 117, 212, 223
228, 387, 405 417, 418, 466 472. 474, 480 483. . . Shimizu, M.*- 095, 184, 318, 431 Shimizu, N.*i 188 Shimoji, K . : 235 Shinoda, K. : 192 Shinozaki, 8. : 239 S h i o i r i , T. : 126, 482 Shiota, T.: 274 S h i r a i , F.: 283 S h i r h a t t i , V.: 440 Shirouchi, Y.: 159 Shobara, 012 Shono, T. : 103, 104, 111 217, 338, 467 Shrock, R.R. : 255 Shroff, H.N.: 117, 377 Shubert, D.C.: 073, 076 Shustermp, A . J . : 180 Shvo, Y . : 082 S i b i , M.P.: 027 S i b i l l e , S.: 026, 222 S i b t a i n , F.: 195, 226 Siddiqui, S.: 291, 350
v.:
S i d l e r , D.R.: 378 S i d o t , C . : 011 Siegneier, R. : 01 7 S i h , C . J . : 042 Sikorski, J . A . : 002 Simon, E.S.: 129, 385 Simon, R.: 339 Simons, R.W.: 366 Simpson, T.H.: 427 Sims, J.J.: 404 S i n c l a i r . P.J.: 298 Singaram, B.: 033, 044, 264 Singh, Singh, Singh, Singh, Singh, Singh,
470
A,*: 281 B.B.: 115, 120 B.P.: 011, 182, 189, 191 H.K.: 245, 279
S.M.: 283, 288 S.P.:
339
526
AUTHORS
Singh, V.: 230 S i n g l e t o n , D. HI: 429 Sipe Jr.: H . J . : 273 Sivavec, T.M.: 019 S j o g r e n , E.B.: 313 S k e l l , P.S. : 190 S k e t , B.; 186, 449 Slough, G.A.: 161 Slougui, N.: 094, 420 S l u s a r s k a , E . : 113 Smegal, J . A . : 178 Smeret, G.: 218 Smigielski* K.: 057 Smit, W.A. : 478 Smith 111, A.B. : 416, 481 Smith, D . J . H . : 104, 156 Smith, 1.J.i 049 Smith, J.2. : 033, 075 Smith, K . :*191 Smith, M.B. : 116, 117, 126 ,182,
261, 377
Smith, R . A . J . : 061 Smith, S.: 121 Smith, T.L. :,455 S n i d e r , B.B. 223, 407, 431 Snieckus, V.": 027, 103, 361 Snyder, J . K . * i 309 So, J . H . 4 445 S o a i , K. : 036, 037, 045
-
090, 318, 330
Sobczak, A , : 306 Sock, 0.: 013 S o d e r q u i s t , J . A . : 066, 465 Solau, D.R.: 067 S o l l a d i e , G.: 436 Sondej, S . C . : 191 Song, Y.H.: 338 S o n n l e i t n e f , B. : 31 8 Sonoda, N. : 058, 077, 092, 097 170, 235, 259, 426 438, 458 Sonoda, T.: 235 Sootome, N.: 266, 276 S o r g i , K.L.: 069 S o r i a , J.J.: 422 S o t e l o , 0.: 408
INDEX
Souppe, J.: 024, 307 Spadaro, A. : 006 S p a g o l o , P.: 380 S p d l t e n s t e i n , 8 . : 374 Spangler, C.W. : 359 S p a t o l a , A.F. : ,021 Speckamp, W.N. : 102, 371, 373 Speranza, G. : 233 Spessard, G.O.: 150 S p i l l a n e , W.J.: 112 Spina, K.P.: 237 S p l e t z e r , E.G.: 291 S p r i n g e r , J.P.: 292, 413, 442 Srebnik, M. : 427 S r i d h a r a n , V.: 362 S r i n i v a s a n , P . S . : 017 S r i v a s t a v a , P.C.: 453 S t a a b , E.: 328 S t a b l e r , R.S.: 422 S t a d l w i e s e r , J. : 428 Stakem, FIG.: 387 S t m , H. : $95, 370 StmOS, I . K I : 398 Stang, P.J. : 281 S t a n t o n , S . A . : 437 S t a r k , S.R.: 447 S t a r n e r , W.E.: 1 1 4 Stavinoha, J I L . : 11 9 Steckhan, E . : 457 S t e e l e , J.: 292 S t e e l e , R.W.: 366 Stegenga, S.: 373 Stehouwer, P.M.: 249 SteinbachI R . : 024, 025, 332 S t e l a , L. :*358 S t e l i o u , K. : 063, 172 Stephens, C . J . : 383 S t e r c h o , Y.P.: 027 S t e r n b e r g , E.Q.: 486 Stevens, R.V. : 125, 369, 461 Stevenson, T.: 089 S t i l l , B. : S t i l l , W.C .'q3308, 309, 41 1 S t i l l e , J . K . : 059, 060, 074 S t i l l e , J.R.:
085, 262, 419, 472 207
INDEX
AUTHORS
S t o d d a r t , J.F.: 037 S t o e s s e l , S.J.: 419 S t o l l , A.T.: 206 Stone, W.B. : 188 S t o r k , G. : 084, 162, 436 S t r i j t v e e n , B.: 323 Stroud, S.G.: 050, 138 Strvchkov, Y.T.: 478 Stucky, G.: 045 Stufflebeme, G.: 094 S t u l t s , J.S.: 444 Siisse, M a :,409 Suarez, E. : 182 Subramanian, L.R. 080 Suda, T.: 211 Suemitsu, R.: 114, 229 Suemune, H.: 460 Sugahara, S.: 282 Sugasawa, T.: 024, 335 Sugawara, T.: 063, 092, 095
*:
2 90
Sugimura, H.4 442 Suginome, H. : 159, 174, 490 S u g i t a , N.: 156 Sugiura, T.: 474, 491 Sugiura, Y.: 042, 342, 348 Suguira, T.: 421 Sugujama, T.: 071 S u i t s , J.Z,: 481 Sukata, K. : 245 Sulmon, P.: 130 S u l t q o v , R.M.: 034, 083 Sumiya, R.: 309 Sumiya, T.: 034, 172, 228 Sundeen, J.: 471 Sur, M.: 055 Surya Prakash, G.K.: 175, 244
302
Suta, L.R.: 350 S u t l e r , M.4.: 318 Suzuki, A. : 063, 076, 265
290, 354, 455 457, 490
Suzuki, H.
527
* : 079,
080, 122
133, 135, 167 189, 190, 195 201, 204, 213 243, 244, 262 270, 333, 41 1 421, 481, 484 Suzuki, K.4 038, 113, 144, 310 Suzuki, N. 248 Suzuki, S . * l 360, 426, 482 Suzuki, Y . : 315, 343 Sviridov, A.F.: 218 S w a d , K . : 419 Swain, C . J . : 219 Swanson, E.D.: 478 Swanson, R.: 119 Sweeney, J.B.: 424 Swindell, C.S. : 068, 071
-
Sychkova, L.;.: 141 Szarek, W.A, : 298 Taber, D.F. : 346, 403 Tabuchi, T. : 199, 251, 331
344, 395
Taddei, M.: 313, 315 r a g a s h i r a , M.: 349 'Tagliavini, E.: 319, 349 Tajima, K . : 008 Tajima, M.: 239 Taka-Oka, $.: 333 Takagi, K . : 834 Takahashi, K . : 009, 058, 351
358, 417, 474, 480
Takahashi, M.: 213 Takahashi, S.: 410 Takahashi, T. : 126 Takahashi# Y.: 075 Takai, K. : 052, 159, 266, 284
328, 341, 324, 343 347, 349, 357, 358 458, 476 Takaoka, K.: 133, 204 Takase, K. : 253 Takayanagi H.: 007 Takechi, K;*: 189 Takeda, A. : 304 Takeda, M.:
120
528
INDM
AUTHSS
Tani, K.*: 389 Takeda, T4*: 246, 327, 433 Tanigawa, Y. : 389 Takei, H. : 442 Taniguchi, H.: 070, 342 Takemasa, T.: 010 Taniguchi, N. : 142 Takemoto, Y.: 337 Takeshita, K.: 077 Tanimoto, Y. : 037 Tapia, R.: 274. Takeuchi, R.: 060, 111, 135 Tarbin, J.A.: 274, 275 391, 396 Takeuchi, S. : 079 Tardella, P.A.: 368 Takeyama, J . : 326, 331 Tardivel, R.: 448 Tarhouni, %.: 168 Takido, T. :,242 T a s s i , D.: 315 Takimto, S. : 141 Tata, C.: 424 Takinami, S. : 457 Tatsmi, T.: 212 Takitoh, N.: 104 Tatsuno, T.: 428 Takujama, N.: 042 Tatsuno, Y. : 389 Tamada, M. : 460 Taufet-Kn6pfel , I. : 320 Tamano, MI: 079 Taufer, I.: 150 Tamao, K. : 027, 033, 205 Tavel, G.: 459 309, 337 Tawarayaqa, Y. : 342 Tamarkin, D.: 261 Taya, K. : 300 TamWu, Y.: 100, 207, 210, 220 Tayano, T.: 354 364, 367, 394, 398 400, 408 Taylor, B.S. : 075 Tamaru, Y.: 428, 471 Taylor, D . A . i 434 Tamblyn, W.H. : 019, 039, 095 Taylor, E.C. :,247, 393 Taylor, R.J.$. : 424, 490 * 352 Taylor, R.T. : 043, 158 Tamborski, C . : 074 Teach, E.G.: 366 T a m , C . : 323 Tenge, B. J. : 374 Tamura, 0 . : 397 Terada, T.: 311 Tamura, R.4 412 Teranishi, S. : 027, 211 Tamura, R. 270, 388, 437 Terao, K.: 102, 365 Tamura, Y.*i 159, 336, 397 Terao, Y.: 1 1 3 Tan, R.P.K.: 359 Terashima, M. 127, 375, 388 an, T.s.: 030 Terashima, S.": 315, 343 Tanabe, M.: 229 Terpinski, J.: 190 Tanate, Y.: 407 Teshima, N.: 203 Tanaka, H.: 013, 072, 233 Teshirogi, J. :,098 285, 342 Tanaka, K.*. 085, 130, 367, 422 Testaferri, L. : 121 Texier-Mullet, F. I 096 Tanaka, M . * i 230, 378, 409 Teyssie, P,: 093 Tanaka, N.: 125 Tezuka, T. : 176 Tanaka, S. : 181 , 393 Thebtaranonth, C . : 257 Tanaka, T.: 205, 307, 309 Thebtaranonth, Y. : 257 Tanaka, Y.: 248, 439 Thianpatanagul, S.: 362 Tanguay, G.: 013, 221 Thiebault, H.: 448 Tani, H.: 079, 195 Thiensathit, S.: 476
-
INDEX
AUTHORS
Thomas, A . P . : 070
Thomas, D.G.: 1 1 4 Thomas, S.E. : 171, 262
Thompson, D.W. : 346, 427 Thompson, P.A.4 161, 342 Thompson, W.J. : 405 Thomsen, I.: 102 Thorat, M . : 409 Thurkauf, 8 . : 324 Tiecco, M. : 171 Tingoli, M. ,071, 171 Tinucci, LI: 313 T i u s , M . A . : 324 Tobito, Y.: 448 Toder, B.H.: 416 Toki, T.: 426 Tokitoh, N. : 122, 386 Tokles, M . : 309 Tolstikov, C.A.4 276 Tomaselli, G.A. : 463 Tomasini , C. : 332 Tcmimori , K . : 320 Tominaga, H.: 212 Tomino, I. :,037 Tcmioka, H. : 214, 456 Tomioka, K . : 463 Tmita, K.: 331, 389, 451 Toofan, J.: 053, 056, 214 Tor, Y.: i91 Torii, S. : 013, 062, 072 219, 233, 237 285, 299, 342 341, 345, 440 Torreilles, E. : 056 Torres, C. : 274 Torssell, K.B.C. : 468 Tortajada, J.: 061 Toru, T. : 399 Toshida, Y . : OQ? Toshimitsu, A. 102, 365 TotZauer, W.: 232 TOUT, J.M.: 006, 407, 474 Toussaint, 0.: 195, 208 Toyoda, H. : 044 Toyoda, M. : 062 Trave, S. : 060
,
.
Traynham, J.E.*: 190 Trimble, L.A.4 296
529
Trimitsis, C. : 224 T r i u z , A.: 483 Trivedi, C.K, : 347 Trombini, C2 : 319, 349 Trost, B.M. ; 083, 098, 210 268, 270, 286 290, 392, 412 413, 420, 441 445, 468, 469 Troupe1 , M. : 01 3, 260 Troyansky, E.I.: 464 Trudell, M.L.: 095 Tsai, D . J . S . : 346 Tsai, Y.-M.: 373 Tseng, C . C . i 070 Tseng, C.K. i 366 Tsien, Y.-L. : 268 T s u b a k i , K.: 408 Tsubata, K.: 111 Tsuboi, Ta. : 056 T s u b i , Ts.: 056 Tsubniwa, N.: 334, 345 Tsuchida, T. : 3 i 7 Tsuchihasbi , C. : 038 Tsuda, T. : 477 Tsuge, S.: 051 Tsugoshi ,,T. : 1 29 T s u j i , J. : 007, 078, 117 151, 195, 212 223, 228, 232 387, 405, 417 418, 421, 466 472, 474, 478 479, 483, 491 Tsuji, M.: 270 T s u j i , Y . : 060, 101, 105, 111 135, 391 , 396 Tsujimoto, K.: 327 Tsukahara, Y.: 488 Tsukamoto, M. : 393 Tsukanaka, T. : 248 Tsukihara, K . : 056 Tsmaki, H.: 332 Tsunekawa. H.: 425
530
Tsmo, Y.: 188 Tilclanantel , W. : 251 Tucker, J . R . i 093 Turner, J. V. * : 329 Tustin, G.C. : 155 Twohig, M.F.: 228 Uang, B.J.: 430 Uchida, K.: 103 Uchida, Y.: 212 Uchikawa, M.: 313 Uchiyama, K.: 273 Uchiyama, M.: 329 Ueda, K . i 062 Ueda, M. : 098, 099, 273 Ueda, W.: 410 Uehara, S . i 460 Uemura, S. : 102, 181, 260 365, 447 Ueno, K . 4 460 Ueno, Y . : 144, 196, 211 272, 345, 448 Uggeri F.: 015, 451 Ugi, IT*:,105, 242 Uguen, I). : 155 Ukai, J.: 254, 433 Ukaji, Y.: 315, 322 Ukita, T.: 212, $67, 359 Umani-Ronchi, A. : 135, 319, 349 Umei, Y.: Oz8 Umemoto, T. : 331, 451 Uneyama, K.: 062, 219, 344, 345 Uno, H. : 484 Uno, M.: 410 Urch, C . J . : 092 Urpi, F.: 099, 104 Urz, R.: 474 ushio, Y.:
INDEX
AUTHORS
020
Utaka, M. : $04 Utimoto, K . : 263, 283, 328 349, 422, 458 Uyaya, S.: 237 Vagberg, J.: 416 Vaccaro, W. : 361 Valderrama,, J.A.: 274 Vallee, D. : 363 Valoti, E.: 313
Van Chiem, P.: g16 Van der Gen, A. : 436 Van Hemelryck, B,: 061 Van Leusen, A.M. : 061, 471 Van Schaik, T. A.M. : 436 Van Schnering, H.-G.: 146 Vanderesse, R. : 082 Vankar, P. : 238 Vankar, P.S.4 160 Vankar, Y .D. 031, 339, 456 Varie, D.L.: i 4 4 Varma, M.: 235 Vam, R.K.: 115 V m a , R.S.: 233, 235, 432 Varney, Y . D . $05 Varvoglis, A. 156 Vatele, J.-M.*i 410 Vaughn, G.D.: 441 Vaultier, M . : 130, 133 Vavilikolanu, P.R.: 238 Vawter, E.J.: 091 Vedejs, E. : 153, 219, 444 Vederas, 3.C. : 296, 364 Veenstra, S.JI: 044 Venanzi, L.M. i 120 Venturello. C . : 176 Verhe, R.: 381 Verlhac, J9-B.: 384, 460 Vermeer, P.*': 249, 438 Vernon, P.: 379 Vessal, B.: 054 Viala, J.: 349 *. Viallefont, Ph. 363, 376, 378 V i d a l , Y.: 215 Viehe, H.G. : 368 Vijayaraghavan, S.T.: 408 Vilapiana, M.3.: 034 Vilarrasa, J. : 099 Villa, C.A. : 475 Villacorta, Q.M. : 146 Villernin, D. 096, 485 Villieras, J. : 168, 420 Vincenti, M.: 304 Viout, P.: 269 Vishwakarma, L.C. : 333 Viswanathan, M.: 075
-
-
.
INDEX
AUTHORS
Vitagliano, A!: 343 VO Q W g , L.: 353 Vo Quang, Y.: 353 Vogel, D.E. : 4x4 Volhann, R.A. : 579 Vollhardt, K.PZC. : 067, 486 Vorbriiggen, H. : 117 Voronkvo, M.G. : 01 6 VOW,
015 Vostrikova, O.S.: 034, 083 Vukicevic, R.: 056 Wtilchli, R.: 109 Wachi, M.: 211 Wada, F. : 078 Wada, M.: 286, 345, 369 Wade, A. R. :,061 Wadia, M.S. : 241 Wakabayashi, S.: 235, 344
G.:
Wakabayashi, Y.: 341 Wakamatsu, K.: 208, 251, 345 Wakamatsu, T.: 363 Wakamoto, K.: 3fi Walbrsky, H.M.
: 237
Waldmann, H . 4 017 Walker, B.J. : 005 Walker, J . C . : 227, 293, 306 walkup, R.D.: 322 Wallace, P.: 095 Waltermire, R.E.: 352 Walters, M.A.: 124 Wag, B.L.4 069 Wang, K.K. : 002, 491 Wang, N.: 032 Wang, P.-C.: 165 Wannamaker, M.W.: 270 Wanner, K . P . : 479 Ward, A.D. : 401, 447 Ward, F.E.: 301 Warin, R.: 093 Warner, P.4 163, 293 Warren, S. : 095, 257, 258 Waseda, T.: 288, Wasserman, H.H. : 461 Watanabe, A.: 240 Watanabe, H. : 248, 290
531
Watanabe, K.*:
188, 244, 290 337
Watanabe, Y .*: 001, 060, 101
105, 111, 135 196, 290, 391 396, 423 Waterhouse, J.: 064 Waterson, 258 Watt, D.S. : 231, 310, 330, 405 WattanasiQ, S.: 217 Wayda, A. : 032
p.:
Weatherford 111, W.D.: 165 Webb 11, R.R.: 101 Webb, M.W./ 165 Webb, T.R. : 118 Weber, G.: 108 Weber, R.H. : 318 Weber, T.: $96 Weber, W.P. : 347 Wegner, G. : 088 Weiberth, F.J.: 131 Weigel, L.9. : 317 Weiler, L. : 418 Weinberger, B.: 013, 221 Weingold, D.H.: 019, 039 Weinig, P.: Og5 Weinreb, S.M. : 318, 371, 375 Weiss, R.: 295, 370 Weiss, U.: 120 Weitzer, H . 4 036 Welch, S . C . : 173 Welker, M.E.: 090, 163, 293 Wells, G.J.: 320 Welvart, Z. : 234 Wenderoth, B.: 024, 025, 332
*
3 3'1)
.JJL
Wenkert, E. : 014, 068, 071, 250 Werner, J.A. : $34 Werstiuk, N.H. : 230 Westermann, J.: 024, 025, 079 Westmijze, H.: 249, 438 Wetzel, J.M. :,032 Wheeler, C.J. : 254 Whelm, J.: 423, 443 White, A.W.: 273 White, S.B.: 273
532
AUTHORS
White, W.L.: 401 Whitesell, J . K . : 057, 230 Whitesell, M.A. : 057, 230 Whitney, S.E.: 091 Whittle, R.R.: 375 Wichelhaus, J.: 153 Wickham, G.: 071 Widdowson, .D.A. : 072, 077, 21 6 Widler, L.4 322 Widmer, U . : 141 Wiemer, D.F.*:’ 051. 224 I.!ieschollek, *R. : 254 Wilbur, D.S. : 188 Wilde, H.: 108 Wilde, R.G.: 444 Wilhelm, R.S.: 076, 091, 092
Williams, D.J.4 037 Williams, D.R. : 046, 396, 427 Williams, L.: 433 Williams, R.M. : 298
Willison, D.: 430 Wilson, J.W.: 033 Wilson, J.W.: 264 Wilson, J . Z . : 046 Wilson, K.D.4 372 Wilson, S.R. : 041, 469, 475 Wilson, W.K.: 294 Winstead, R.C.: 427 Wittenberger, S.: 444 Woell, J . B . : 139, 153, 155, 156 Wolf, R.: 457 Wolff, M . : 018 Wollmann, T.A.: 322 Wolsieffer, L.A.: 032 Woltermann, A.: 302 Wong, G.S.K.: 103 Wong, H.: 123 Wong, S.: 002 Wonnacott, A.: 025 Wright, B.T.: 229 Wright, S.W.: 152 Wrobel, J.E.: 030 Wroble, R.R.: 231 WU, P.-L.: $71 Wuest, J.D. : 022 Wulff, G.: 1.53
INDEX
* : 321, 325, * 442, 462 P.G.M. : 161, 342
Wulff, W.D.
Wuts, Wymann, W.E.: Xu, Y.: 380 Xu, Z.: 069 Yahata, Yakura, Yamada, Yamada, Yamada, Yamada, Yamada,
413
113
N.: 058 T.4 336 K . : 120, 216, 395, 490 M.: 478 S.: 159, 174 T.4 246, 309 Y. : 071, 100, 210 220, 337
Yamagata, T.: 389 Yamagata, Y.: 389 Yamagkuchi, MI: 331 Yamaguchi, M. : 030, 147, 199 251, 285, 288 297, 305, 312 313, 344, 395
393
Yamaguchi, R.: 303 Yamaji, T.: g48 Yamakawa, K . : 220, 237, 338
384, 409
Yamakawa, Y.: 423 Yamamoto, A . i 478 YamamOto, H. : 031, 038, 039 096, 129, 283, 326, 433, 485 Yamamoto. J. : 056
*
Yamamoto;
064, 128, 254, 287,
K . 4 007
122 192 284
339
YamamOto, M.*: 395 Yamamoto, T.*: 102 Yamamoto, Y . : 075, 092, 210 213, 318, 343 369, 391, 396 Yamamura, K. 433, 484 Yamamura, Y. 129 Yamana, Y.: 07, 157 Yamanaka. Y . 3 42 Yamanoi, T.: 036, 037, 318, 330
INDEX
AUTHrnS
Yamasaki, H.: 144 Yamasaki , Y. :,058 Yamashita, A.,: 205
Yamashita, J. 070, 201, 255 Yamashita, M.*I 114, 184, 229 Yamashita, S.: 285, 342 Yamashita, T.: 128 Yamashita, Y.: 072 Yamato, T.: i75 Yamauchi, T. : 014 Yamawaki, K.: 211
Yamazaki, N.: 036 Yamazaki, S.: 315 Yamazaki, Y.: 239, 366 Yanagi, K.: 400 Yanagi, T.: 003 Yanagihara, N.: 422 Yanai, T.: 180 Yang, D.C.: 325, 413 Yangs J.: 359 Yang, s.: 200 Yang, T.-K.: 114 Yang, Y.-L.: 439
Yang, z-Y.: 001 Yao, K.: 221 Yashunsky, D.V.: 218 Yasuda, H.4 232, 397 Yasuda, M. : 128
Yasmura, M.: 052
Yasunaga, H.: 047, 461 Yatagai, H.: 343 Yates, S.W.: 165 Yates, K.: 168
Yen, S.-J.: 070 Yevich, J.P.: 131
Y i , K.Y.: 136 Y i , Q.: 244 Y i j u n , C.:,365 Yoakim, C . : 029, 046, 048 Yoda, H. : 422 Yogo, T. : 063 Yokoo, K.: 342 Yokoyama, M.: 084, 183, 326
342
Yokoyama, S.: 045 Yokoyama, T.:
093
533
Yokoyama, Y.: 075 Yon, G.H. :,086 Yoneda, F. : 085 Yoneda, R . 4 482 Yoneda, S. : 302
Yonemitsu,,O.: 014 Yoon, 'N.M. : 022, 051 Yoon, V.C.:,119 Yoshida, Yoshida, Yoshida, Yoshida,
J. : 268, 492, 445
S.: 239, 243 T. 065, 211
105, 243 100, 207, 260 220, 364, 367 394, 398, 400 ,408, 428, 471 Yoshikawa, S. : 144
Y.'. Yoshida, Z.*I
Yoshi kawa, T. :,120 Yoshikoshi, A. : 303
Yoshimura, N.: 020 Yoshinaga, Y,: 327 Yoshioka, H. : 184 Yoshitake, M.: YOU, M.: 279
395
Youn, I.K.: 086
Young, C.G.4 215 Young, R.N. : 030, 145 Youngdahl , K. : 040 Yu, L.-C.: 432 Yuba, K . : 305 Yue, S. : 362 Yuhara, M.: 483, 491 Yukawa, T.: 440 Y u k i z a k i , H.: 068 YUS, M.: 110, 224, 251, 252
267, 308, 370, 448
Zacharie, B. : 022 Zahalka, H.A.: 035
Zahra, J.-P.: 281 Zakrzewski, J.: 256 Zanirato, P. : 134
Zanirato, V.: 471, 483 Zappi, G.D.4 011 Zard, S.-Z. : 029, 129, 181 Zaugg,
H.E.
*
:
234, 385 112
534
Zefirov, N.S.*: 367 Zelle, R.E.: 295 Zenki, S.: 274 Zezza, C . A . : 116 Zhai, D. : 298 Zhang, S.: 419 Zhang, Y.-A,: 072 Zheng, J.: 412 Ziegler, F.E. : 249 Zinov'eva, L.V. : 067 Zocher, D.H.T. : 399 Zorc, B.: 214 Ziiger, M.F.: 318 Zucker, P&: 475 Zupan, M. :,186, 449 Zweifel, C. i 282, 289 Zwierzak, A. : 113 Zyk, N.V. : 367
AUTHORS
INDEX
