Compendium of Organic Synthetic Methods
Compendium of Organic Synthetic Methods Volume 4 LEROY G.WADE, Jr.
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Compendium of Organic Synthetic Methods
Compendium of Organic Synthetic Methods Volume 4 LEROY G.WADE, Jr.
DEPARTMENT OF CHEMISTRY COLORADO STATE UNIVERSITY FORT COLLINS, COLORADO
A Wiley-lnterscience Publication
JOHN WILEY & SONS, New York
Chichester
Brisbane
Toronto
Copyright0 1980 by John Wiley 8 Sons, Inc. All rights resewed. Published simultaneously in Canada.
No part of this book may be reproduced by any means, nor transmitted, nor translated into a machine language without the written permission of the publisher. Library of Congress Catalog Card Number:71-162800 ISBN 0-471-04923-9 Printedin the United States of America. 10 9 8 7 6 5 4 3 2 1
CONTENTS ABBREVIATIONS
ix
INDEX, MONOFUNCTIONALCOMPOUNDS
xi
INDEX, DIFUNCTIONAL COMPOUNDS
xii
INTRODUCTION
xiii
1 PREPARATIONOF ACETYLENES
1
2 PREPARATIONOF CARBOXYLIC ACIDS, ACID HALIDES,
AND ANHYDRIDES
9
3 PREPARATIONOF ALCOHOLS AND PHENOLS
28
4 PREPARATIONOF ALDEHYDES
73
5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS
102
6 PREPARATION OF AMIDES
135
7 PREPARATION OF AMINES
146
8 PREPARATIONOF ESTERS
176
9 PREPARATION OF ETHERS AND EPOXIDES
198
10 PREPARATIONOF HALIDES AND SULFONATES
215
11 PREPARATIONOF HYDRIDES
235
12 PREPARATIONOF KETONES
252
13 PREPARATION OF NITRILES
297
14 PREPARATIONOF OLEFINS
309
15 PREPARATIONOF DIFUNCTIONALCOMPOUNDS
340
PREFACE By their compilation of Volumes 1 and 2 of this Compendium, Ian and Shuyen Harrison filled one of the greatest needs of the synthetic community: a method for rapidly retrieving needed information from the literature by reactiontype rather than by the author’s name or publicationdate. Compendiumof Organic Synthetic Methods, Volume 4, presents the functional group transformations and difunctional compound preparations of 1977, 1978, and 1979. We have attempted to follow as closely as possible the classificationschemes of the first three volumes; the experienced user of the Compendium will require no additional instructions on the use of this volume. Perhaps it is fitting here to echo the Harrisons’ request stated in Volume 2 of the Compendium: The synthetic literature would become more easily accessible and more useful if chemists could write well-organized, concise papers with charts and diagrams that allow the reader to assess quickly and easily the scope of the published research. In addition, the reporting of actual, isolated yields and detailed experimental conditions will save a great deal of wasted effort on the part of other chemists hoping to apply the reported reactions to their own synthetic problems. I wish to express my gratitude to the many people who helped to bring this book to completion: To Mrs. JoAnn Barley for her patience and dedication in the typing of the camera-ready copy; to Roy Smith, James McKearin, and Jon Lawson for proofreading the manuscript with great care and offering hundreds of helpful suggestions; and to my wife Betsy for her patience and moral support throughout the arduous preparation of this Compendium. Fort Collins, Colorado
LEROY G. WADE,JR.
September, 1980
V
ABBREVIATIONS An attempt has been made to use only abbreviations whose meaning will be readily apparent to the reader. Some of those more commonly used are the following: Ac Am Ar
9-BBN Bu BZ
CP DBU DCC DDQ DEAD DIBAL (DIBAH) DMAD DME DMF DMSO Et Hex HMPA, HMPT hv L LAH LDA MCPBA Me MEM Ms MVK NBS Ni @ Ph PPA
Acetyl Amy1 Awl 9-borabicyclo[3.3.1 Inonane Butyl Benzyl Cyclopentadienyl 1,5-diazabicyclo[5.4.O]undecene-5 Dicyclohexylcarbodiimide 2,3-Dichloro-5,6-dicyanobenzoquinone Diethyl azodicarboxylate Diisobutylaluminum hydride Dimethyl acetylenedicarboxylate 1,P-Dimethoxyethane Dimethylformamide Dimethyl sulfoxide Ethyl Hexyl Hexamethylphosphoramide (hexamethylphosphoric triamide) Irradiationwith light Triphenylphosphineligand (if not specified) Lithium aluminum hydride Lithium diisopropylarnide meta-Chloroperbenzoic acid Methyl p-MethoxyethoxymethyI Methanesulfonyl Methyl vinyl ketone N-bromosuccinimide Raney nickel Polymeric backbone Phenyl Polyphosphoric acid
X
PPE Pr Py, Pyr Sia Tf TFA TFAA THF THP TMEDA TMP TMS Ts
A
ABBREVIATIONS
Polyphosphate ester Propyl Pyridine secondary-isoamyl Trifluoromethanesulfonate Trifluoroacetic acid Trifluoroacetic anhydride Tetrahydrofuran Tetrahydropyranyl Tetramethylethylenediamine 2,2,6,6-Tetramethylpiperidine TrimethylsiIyl p-Toluenesulfonyl Heat
E.
Miscellaneouscompounds
Oletins
Nitriles
Ketones
Hydrides (RH)
Halides,sulfonates,sulfates
Ethers, epoxides
Esters
Amines
Amides
Alkyls, methylenes, aryls
Aldehydes
Carboxylic acids, acid halides, anhydrides Alcohols, phenols
Acetylenes
I
14 7
12 6
10 5
5
8
4 3
1 1
29 21 30 22
25 19 26 19 27 20
23 15
16 9 17 9 18 12 19 13
44 59
36 36 37 37 38 38 39 39 40 44 41 46 42 48
29
34
31 28 32 28
94
60
59 92
74 118
90 145
144
88
61 102 47 62 77 73 103 135 4 8 6 3 76 104 49 64 79 82 105 137 50 83 51 66 81 84 106 138 52 82 84 140 53 68 83 86 107 141 54 69 84 86 107 141 55 70 85 87 109 142 56 71 86 90 113 142 57 72 87 90 115 143 102 158 103 160 104 161 105 161
96 150 97 154 98 155 99 156 100 156
148
94
93 146
119 196 120 197
134 209 135 214
111 188 112 189 113 128 189 205 114 129 191 206 115 130 191 206 116 192 117 132 194 208
107 176 108 123 182 198 109 124 186 203
166 181 136 215 252 297 137 152 167 217 235 253 138 153 168 217 236 257 139 169 184 221 264 298 140 155 170 222 239 266 186 301 142 157 172 187 223 239 268 303 158 173 188 241 269 303 144 159 174 225 242 270 145 160 175 190 226 243 271 303 146 176 191 227 274 305 147 177 192 230 275 306 163 193 250 306 149 179 194 231 282 307 150 165 180 195 233 251 284 307 207 331 208 335 209 336 210 337
202 323 203 323 204 324 205 327
198 314 199 317 200 320
196 309
Sect. 15A 30A 45A 60A 90A 105A 120A 180A 210A
Blanks in the table correspondto sections for which no additional examples were found in the literature.
Acetylenes Carboxylic acids Alcohols, phenols Aldehydes Amides Amines Esters Ketones Olefins
(PROTECTION] Pg. 8 22 63 95 145 165 197 287 338
INDEX,DIFUNCTIONALCOMPOUNDS
Sections-heavy type Pages-light type
315 352
325 367
317 359 318 360
327 370 328 372
309 345 310 347
320 361
330
348
362
306 344 307
344
403
410
415
412 355 413
420 361 429
440
413
430
441
337 391
375 331 381
339 392 340 394
382
395
407
448 370 456
465 373 474
457
475
490
Blanks in the table correspondto sections for which no examples were found in the literature.
xii
493
INTRODUCTION Relationship between Volume 4 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 4 presents over 1000 examples of published methods for the preparationof monofunctional compounds, updating the 5000 in Volumes 1,2, and 3.In addition, Volume 4 contains over 1000 additional examples of preparations of difunctional compounds and various functional groups, updating these sections which were initially introduced in Volume 2. The same systems of section and chapter numbering are used in all four volumes. Classification and Organization of Reactions Forming Monofunctional Compounds. Examples of published 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 listed in a somewhat arbitrary order, although an effort has been made to put similar reactions together when possible. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation, which appears in both starting material and product, or increases or decreases in the length of carbon chains; for example, the reactions t-BuOH -+ t-BuCOOH, PhCH,OH + PhCOOH and PhCH=CHCH,OH + PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohois. Entries in which conjugate reduction or alkylation of an unsaturated ketone, aldehyde, ester, acid, or nitrile occurs have generally 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, RCH,-H -+ RCH,COOH (carboxylic acids from hydrides), RMe -+ RCOOH (carboxylic acids from alkyls), RPh + RCOOH (carboxylic acids from aryls). Note the distinction between R,CO -+ R,CH, (methylenesfrom ketones) and RCOR’ + RH (hydrides from ketones). Alkylations which involve additions across a double bond are found in section 74, Alkyls from Olefins.
xiii
XIV
INTRODUCTION
The following examples illustrate the application of the classification scheme to some potentially confusing cases: RCH=CHCOOH +. RCH=CH, RCH=CH, -+ RCH=CHCOOH ArH + ArCOOH ArH -+ ArOAc RCHO + RH RCH=CHCHO -+ RCH=CH, RCHO + RCH, R,CH, + R,CO RCH,COR + R,CHCOR RCH=CH, -+ RCH,CH, RBr RC=CH + RC=CR
+ ROH + RCOOH + RCOOR
RCH=CHCHO + R,CHCH,CHO RCH=CHCN +. RCH,CH,CN
(hydridesfrom carboxylic acids) (carboxylicacids from hydrides) (carboxylic acids from hydrides) (esters from hydrides) (hydrides from aldehydes) (hydrides from aldehydes) (alkyls from aldehydes) (ketonesfrom 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)
Reactions are included even when full experimental details are lacking in the given reference. In some cases the quoted reaction is a minor part of a paper or may have been investigatedfrom a purely mechanistic aspect. 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. xi, which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes; Section 2, acetylenesfrom 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 the reactions of acetylenes that form other 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, which lie 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 and phenols from alcohols and phenols. Alkyiations which involve conjugate additions across a double bond are found in section 74, Alkyls from Olefins.
INTRODUCTION
xv
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 on olefins from aldehydes and Section 207 on olefins from ketones. Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and olefins are also indexed on p. xi. The pairs of functional groups alcohol, ester; carboxylic acid, ester; amine, amide; carboxylic acid, amide can be interconvertedby quite trivial 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. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. The references 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, aldehyde, amide, amine, ester, ether, epoxide, 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 of the groups do not affect the classification. Thus preparations of 1,2-aminoalcohols, 1,3aminoalcohols and 1,4-aminoalcohols are included in a single section. The following examples illustrate the application of this classification system:
DifunctionalProduct
Section Title
RC=C-C=CR RCH(0H)COOH RCH=CHOMe RCHF, RCH(Br)CH,F RCH(OAc)CH,OH RCH(0H)COOMe RCH=CHCH,COOMe RCH=CHOAc
Acetylene-Acetylene Carboxylic Acid-Alcohol Ether-Olefin Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Olefi n Ester-Olefin
How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xii gives the section and page corresponding to each difunctional product. Thus Section 327
xvi
INTRODUCTION
(AlcohoCEster) contains examples of the preparation of hydroxyesters; Section 323 (Alcohoi-Alcohol) contains examples of'the preparation of di01s. 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 (monofunctionalsections) or Carboxylic acid-Olefin (difunctional sections). 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 monofunctional compounds. Thus the reaction RCI + ROH can clearly be extended to the preparation of diols by using the corresponding 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 acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by quite trivial 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, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 1
PREPARATION OF ACETYLENES Section 1 Acetylenes from Acetylenes
B + 3 Ph-C-CH
electrolysis
TH F
3
C-C-Ph
70%
Chem Lett, 999 (1977)
i-Bu3A1
+
*-.
N i (Mesal)2
n-Bu-CXBr
pentane
1-B u - C=.C --n- Bu
70%
Tetr Lett, 2831 (1978) C5H1 CECZnCl 93%
NC
--@ 0r
JOC 1
43,
358 (1978)
2
SECTION 2
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1) BuBr
*
LiCH2C-C-Li
BuCH2CzCBu
30%
2 ) BuBr/HMPT JCS Perkin I,1218 (1979)
NaNH2
Bu-CX-CH2CH20H
91%
H C X ( CH2) 60H
H2N( CH2 13NH2
Rec Trav Chim 96, 160 (1977) L
Me
-
Me
PdCl 2L2
CuI, E t 3 N
Me
Me
+ Ph-CECH
Section 2
Chem Pharm B u l l
Acetylenes from Carboxylic Acids
No a d d i t i o n a l examples
26,
3843 (1978)
SECTION 4
Section 3
3
ACETYLENES FROM ALDEHYDES
Acetylenes from Alcohols
No a d d i t i o n a l examples Section 4 Acetylenes. from Aldehydes
Ar-CHO 2)
*
*
Ar-C-CH
up t o 90%
Ar = p y r r o l e , furan, azulene, e t c . Angew I n t Ed 17, 609 (1978) c
8
t-BuOK, (Me0)2PCHN2
*
Ph-CH2 CHO
Ph-CH2-C-CH
TH F JOC 44, 4997 (1979)
80%
4
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 5
_Acetylenes from A l k y l s . Methylenes and A r y l s
No Examples Section 6
Acetylenes from Amides
No add: ti onal examples Section 7
SECTION 7
AcetYlenes from Amines
No a d d i t i o n a l examples
SECTION 10
Section 8
ACETYLENES FROM HALIDES
5
Acetylenes from Esters
1 ) BuLi COOMe 54%
2) C1 P03Ph2 base 3 ) Nay NH3
JACS Section 9
100,4852
(1978)
Acetylenes from Ethers
No examples S e c t i o n 10
Acetylenes from Hal i d e s
C5H1 C-CZnC1
t
PdL4 NC@ -
c5H1 cx+N
r JOC
43,
358 (1978)
93%
6
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 12
1) BuLi
I
LiCHC12
\
Ph
CH2Br
-
Synthesis, 502 (1979)
BuLi
Et-CH2CF3
Et-C-C-Bu
73%
T e t r L e t t , 3103 (1978)
Section 11
Acetylenes from Hydrides
No examples For examples o f t h e r e a c t i o n RCzCH (Acetylene
-
Section 12
+
RCEC-CzCR'
see s e c t i o n 300
Acetyl ene) Acetylenes from Ketones
0
II
*
Ph-C-CH2Et
Ph-C-C-Et
Et3N, CH2C12 Chem L e t t , 481 (1979)
50%
ACETYLENES FROM OLEFINS
SECTION 14
-
fi
7
Me3Si CHN2
/"\ Ph Ph
Ph-CEC-Ph
80%
BuLi
JCS P e r k i n I , 869 (1977)
CEC-
65%
pyr, r e f l u x JOC 44, 4116 (1979)
8 Ph-C-CH-SMe I
Me
1 ) H2NNHTs
P h- CX-Me
90%
2) MeLi
Synthesis, 305 (1978)
S e c t i o n 13
Acet.ylenes from N i t r i l e s
No examples S e c t i o n 14
Acetylenes from O l e f i n s 1 ) LiA1H4, TiC14 t
HCzC
2 ) CH2=C=CHBr, CuCl Chem L e t t , 789 (1978)
54%
8
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 15
SECTION 15A
Acetylenes f r o m M i scell.aneous Compounds
No a d d i t i o n a l examples S e c t i o n 15A
P r o t e c t i o n o f Acetvlenes
Use o f t h e T r i m e t h y l s i l y l group t o t e r m i n a t e polyeneynes of t h e f o r m -(CH=CH)nrCzC-TMS.
S t a b l e t o G r i g n a r d reagents e t c . , b u t
removed by aqueous base. 34, 1037 (1978) Tetrahedron -
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 2
PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES Sec t i on 16
Carboxyl ic Acids f r o m Ace t y l enes
KMn04, H20 BuCX-H
CH2C1
Bu-COOH
, Adogen
61 %
Synthesis , 462 (1978) S e c t i o n 17
Carboxylic Acids and Acid Halides f r o m Carboxyl i c Acids
96% ee
JOC 44, 2250 (1979) 9
10
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
COOH
SECTION 17
m o d i f i e d Arndt-Ei s t e r t
COOH 94%
T e t r L e t t , 2667 (1979)
R-CH2COOH fatty
acid
1 )LDA,THF
I
R-CH -COOH
bH
2)02 ,HMPA
Cr03,NaI04 AcOH/H20
-58%
R-COOH
Synth Comm
2,
63 (1979)
Review: "Synthesis o f Aldehydes, Ketones, and Carboxylic Acids from Lower Carbonyl Compounds by C-C Coupling Reactions" Synthesis, 633 (1979) Carboxylic Acids may be a l k y l a t e d and homologated v i a ketoacid, k e t o e s t e r and o l e f i n i c a c i d intermediates.
See s e c t i o n 320
( C a r b o x y l i c Acid - Ketone), s e c t i o n 360 ( E s t e r Section 322 (Carboxylic Acid
-
Olefin).
-
Ketone) and
Conjugate reductions o f
unsaturated acids are l i s t e d i n Section 74 ( A l k y l s from O l e f i n s ) .
SECTION 17
11
CARBOXYLIC ACIDS AND A C I D HALIDES FROM CARBOXYLIC ACIDS C1\NpN/C1
kB
R-COOH
N I c1
18
R-C-C1
Et3N
T e t r L e t t , 3037 (1979)
-A F'
Me2C=CNMe2
R-COOH
100%
R-C-C1
R = C13C, t-Buy HCO, furan-2-yl, e t c . Chem Corn, 1180 (1979)
0
CF3CF2CF=0
R J - OH
0 RJ-F
*
80-90%
Chem L e t t , 483 (1977)
il Ph-C-C1
polyethylene g l y c o l KF, CH3CN
*
PI
Ph-C-F
Chem L e t t , 283 (1978) Review:
" A c t i v a t i o n and P r o t e c t i o n o f t h e Carboxyl Group" Chem & Ind, 610 (1979)
98%
12
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 18
SECTION 18
C a r b o x y l i c Acids f r o m A l c o h o l s
K2 (Ru 04 )
86%
persulfate JCS Chem Comm, 58 (1979)
Pr-CH20H
electrolysis
N i (OH)2anode
+
Pr-COOH
92%
Synthesi s , 513 ( 1 979)
Bu4NMn04 p y r i d i ne
*
6
JCS Chem Corn, 253 (1978)
98%
SECTION 19
CARBOXYLIC A C I D S AND A C I D HALIDES FROM ALDEHYDES
S e c t i o n 19
C a r b o x y l i c Acids and A c i d H a l i d e s f r o m Aldehydes
13
0
II
1 )NaH ,( E t O)*PCH (CN)O-t-Bu -
C6Hl 3CH0
2)ZnC12,Ac20
e
C6H13CH2COOH
95%
0
3) OH JACS 99, 182 (1977)
n-C5H, CHO
e Q BzEt3NMn04 CH2C1
*
89 %
C5H,,COOH
Monatsh Chem 110, 1471 (1979)
00
Bu4NMn04
99%
c1
c1
*$
JCS Chem Corn, 253 (1978)
N i c k,NaOH H20 el peroxide
N02
96%
N02 Chem Pharm B u l l 26, 299 (1978)
14
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
'sHl
3-\<3 1 )NBS
2)Zn/ZnC12
H
SECTION 19
60%
C 6 H l 3-COOH
JOC 43, 3417 (1978)
0'"" NBS
>82%
hv
(converted t o e s t e r ) T e t r L e t t , 3809 (1979) PhCHO t
r9
FeCl
PhCCl
Ph-C-C1 w
+
-80%
PhCHCl J Gen Chem (USSR) 4 7 , 1531 (1977)
Related methods: Also v i a : Esters
-
Carboxyl i c Acids from Ketones (Section 27). Section 109.
SECTION 23
CARBOXYLIC A C I D S AND A C I D HALIDES FROM ESTERS
Section 20
D r b o x v l i c Acids from A1 k y l s
15
No a d d i t i o n a l examples Section 21
Carboxvlic Acids from Amides
No a d d i t i o n a l examples
Section 22
Carboxvlic Acids from Amines
No a d d i t i o n a l examples Section 23
Carboxyl i c Acids and Acid Hal i d e s from Esters
s
R-C-OR'
1 )Me3Si I,CC14 2) H p
R = a1k y l , a r y l
*
RCOOH + R ' I
80-95%
, heterocyclic
R ' = Me, E t JACS
99, 968
(1977)
16
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 23
COOMe 1)C1SiMe3, NaI
86%
2) H20 JCS Chem Comm, 874 (1978)
0 Me3C-!-OMe
C1S i Me3
Me3C-COOH
w
Na I
79%
JOC 44, 1247 (1979)
PhCH2-COOEt
1 ) Me3SiS iMe 3/ I
2 ) H20
e
PhCH2COOH
95%
-
Angew I n t Ed 18, 612 (1979) BZ-C02Et
Ph-COOMe
I 2 ,PhSiMe
3
BZ-COOH
EtSH
A1 B r 3
96%
Synthesis, 417 (1977)
Ph-COOH
T e t r L e t t , 5211 (1978)
94%
SECTION 2 3
CARBOXYLIC A C I D S AND A C I D H A L I D E S FROM ESTERS
17
97% COOMe
COOH
JOC 44, 4727 (1979)
0 I
Ph-hMe
2 L-BuOK,
1 H20
*
JOC 0 II
Me2 Cu L i
R-C-O-CH2CH=CH 2
*
Ao
Ph-C-0
42,
100%
918 (1977)
0 II
R-C-OLi
75-85%
R = al kyl , aryl S y n t h Comm 8, 15 (1978)
1) H S ( O A c ) 2 2 ) KSCN
*
R-COOH
T e t r L e t t , 2081 (1977)
%90%
18
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
NaSePh
SECTION 24
100%
T e t r L e t t , 4365 ( 977 Other r e a c t i o n s u s e f u l f o r t h e h y d r o l y s i s o f e s t e r s may be found i n S e c t i o n 30A ( P r o t e c t i o n o f C a r b o x y l i c A c i d s ) .
Me I
CH3(CH2)5C02;i -L-Bu Me
0 (coc1)* II CH2 ) 5C-C1 3 DMF CH3
JOC 43, 3'372 (1978) S e c t i o n 24
C a r b o x y l i c Acids f r o m E t hers
No a d d i t i o n a l examples
92%
S E C T I O N 26
CARBOXYLIC ACIDS FROM HYDRIDES
S e c t i o n 25
19
C a r b o x y l i c Acids and A c i d H a l i d e s from A l k y l H a l i d e s
4 0
II
(Me3Si)*0
84%
c1
c1
JCS Chem Corn, 808 (1977)
Also v i a :
Esters
S e c t i o n 26
-
S e c t i o n 115
C a r b o x y l i c Acids from H y d r i w
1 ) LDA ,THF
90%
2)(Me0)2C0
OMe
OMe Synthesis, 245 (1977)
20
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 27
Q
-Carboxylic
SECTION 28
Acids from Ketones
8
1 ) NaH, (Et0)2PCH(CN)O-t--Bu 2) ZnC12, Ac20
3) OOH JACS
6
99, 182
~~70%
(1977)
Review: "Synthesis of Aldehydes, Ketones, and Carboxylic Acids from Lower Carbonyl Compounds by C-C Coupling Reactions" Synthesis, 633 (1 979) Also via: Esters Section 28
-
Section 117.
@rboxylic
No additional examples
Acids from Nitriles
CARBOXYLIC A C I D S FROM OLEFINS
SECTION 29
S e c t i o n 29
21
C a r b o x y l i c Acids from O l e f i n s
C8H1 7-CH=CH2
KMn04 ,HOAc
94%
w C8H17-COOH
H2°
JOC 42, 3749 (1977) 1 ) 03
n -C6H1 3CH=CH2 2 ) H2/Pd, CaC03, PbO
JOC (USSR)
n-C H COOH 6 13
14,48
(1978)
98%
2 ) H2, L i n d l a r B u l l Akad USSR Chem
2)NaI04 ,NaHC03 HO
3 , C6H13NH29 A 4 ) KOH, H20
81%
25,
*
H e l v Chim Acta
1790 (1977)
77%
61,2286
(1978)
22
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL
S e c t i o n 30
4
SECTION 30A
Carboxyl ic Acids from M i s c e l l aneous Compounds Li I 1) PhOCHCOOLi 2 ) NaOH, H202
*
Bu3B
Bu-CH2COOH
100%
T e t r L e t t , 2891 (1978)
1 ) BuMgBr, N i C l 2THF
2 ) H+J
0
Ph U
O
92% 99%ee
he BCS Japan 51, 3368 (1978) c
Section 30A
P r o t e c t i o n o f Carboxylic Acids
1 ) KOH
2 ) C1 CH2SMe, NaI , 18-crown-6
*
R-COOH
H
w
0
It
R-C-OCH2SMe
1 ) NH4Mo03, H202
o r CH31 T e t r L e t t , 731 (1978) T e t r L e t t , 689 (1979)
PROTECTION OF CARBOXYLIC ACIDS
SECTION 30A
23
9, 267 (1979) Synth Corn -
1) BrZnCH2COOEt
+
Y
O Br O
H
/yPI
2 ) H2C(OMd2
88% ocH20cH3
Br
S y n t h e s i s , 567 (1977) CHzCH2SCH3 CH2CH2SCH3
H2N-CH-COOH I
TsOH, C1 3C-CH20H
*
8
I
H3N-CH-l-OCH2CCi
CC14, a z e o t r o p i c d i s t .
ooTs
60%
S y n t h e s i s , 24 (1979)
PhCH2CH2COOH t
EtSH
DEpC
8
PhCH2CH2C-SEt
85%
Et3N, DMF
Chem Pharm B u l l 25, 2423 (1977)
24
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
9Ph MeCH-COOH
DMPADC ,Et3N
OPh
*
E t S H ,DME
SECTION 30A
1,4
100%
Me-CH-C-SEt
Synth Comm 9, 91 (1979)
51
1 ) Ph2PC1 , E t 3 N Z-gyl -OH
>
2 ) PhSH
Z-gly-SPh
Synth Corn
1,4-cyclohexadienelPd-C
0
II
(1977)
removes b e n z y l e s t e r p r o t e c t i n g groups.
JOC
R-C-OBZ
7 , 251
98%
A1 C1
b
43,
4194 (1978)
R-COOH
PhOCH3
T e t r L e t t , 2793 (1979)
peptide
-
25
PROTECTION OF CARBOXYLIC A C I D S
SECTION 30A
*
Bzl
peptide-OH
Pd/ C JCS p e r k i n I,490 (1977)
Na2S
R-COOH
TH F
R = Azetidinone JOC 43, 1243 (1978)
0
II
R-C-OCH2CH2X
NaHSe
RCO8
o r 1 ) Me3SnLi
2 ) Bu4NF X = C1 , B r
fi pep t ide -C-0- CH2 - CH2Br
Synth Comm 1) NaI , DMF
*
g,
301 and 359 (1978)
peptide-COOH
2) Zn Chem Ber
112,2145
(1979)
26
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 30A
Use o f t h e e-methoxyphenacyl a c i d p r o t e c t i n g group i n g i b b e r e l l i n synthesis.
S t a b l e t o Koenigs-Knorr c o n d i t i o n s
, Mn02
oxidation, etc.
Removed by p h o t o l y s i s i n e t h a n o l o r by Zn/HOAc. 34, 345 (1978) Tetrahedron -
1) t e t r a m e t h y l g u a n i d i n e , CH3COCH2COOEt,
H-Phe-OH
DMF
*
H-Phe-ONbzl .HC1
2 ) Nbzl-Br
88%
3 ) HC1, MeOH 31, 1865 (1978) Aust J Chem -
77% 8 , 515 (1978) Synth Comm -
Use o f i m m o b i l i z e d carboxypeptidase Y ( a t pH 8.5) t o remove e t h y l e s t e r b l o c k i n g groups i n p e p t i d e s y n t h e s i s . JACS 101, 3394 (1979)
SECTION 30A
PROTECTION OF CARBOXYLIC A C I D S
27
Use o f Maq e s t e r s i n pept ide synt h e s i s : 0 Prepared using Maq-OH and DCC; removed by sodium d i t h i o n i t e , p h o t o l y s i s , o r polymer-bound 9,l O-di hydroxyanthracene. Soluble i n organic solve n ts , and UV-active a l l o w i n g f a c i e d e t e c t i o n on TLC. T e t r L e t t , 103
Review:
(1 977)
" A c t i v a t i o n and P r o t e c t i o n o f t h e Carboxyl Group"
Chem & I n d , 610 (1979) Rev ew:
" P r o t e c t i n g Groups
n Peptide Synthesis"
Chem & Ind, 617 (1979)
Other r e a c t i o n s useful f o r t h e p r o t e c t i o n o f c a r b o x y l i c a c i d s a r e i n cluded i n Section 107 (Esters from Carboxylic Acids and Acid H a lides) and Section 23 (C a rb o x y l i c Acids from E s t e r s ) .
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 3
PREPARATION OF ALCOHOLS AND PHENOLS Section 31
Alcohols from Acetylenes
hv
OH
JACS 99, 5192 (1977) Section 32
Alcohols from Carboxylic Acids and Acid Halides
JCS Chem Comm, 330 (1978)
“3 NaBH4
CH3( CH2)14-C-O-N
CH3 ( CH2), 4-CH20H
0
Chem L e t t , 981 (1979)
28
69%
SECTION 34
ALCOHOLS FROM ALDEHYDES
0
U
MeO-CCH2CH2CC1
NaBH4- A1 203
0 II
MeO-C-CH 2CH2 CH2 OH
29
80%
Synthesis, 912 (1979) Also v i a :
Section 33
Esters ( S e c t i o n 38)
Alcohols from Alcohols
No a d d i t i o n a l examples
S e c t i o n 34
n-C5H1,-CH0
Alcohols from Aldehydes
Na2S204
~
n -C5H1
CH20H
63%
H20/di oxane Synthesis, 246 (1977)
n-C H CHO 9 19
2-propanol a1 umi na
n-C H CH OH 919 2
JOC 42, 1202 (1977)
84%
30
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 34
,CH20H
CHO
I
NaH/t-AmONa -
98 %
JOC 43, 4804 (1978)
Bu3SnH
CH3 ( CH2 )6CH0
CH3 ( CH2)&H20H
s i l i c a gel
90%
JOC 43, 3977 (1978)
CH3( CH2)7CH0
Cp2Zr (C1 )BH4
+
CH3(CH2)8-OH
90%
T e t r L e t t , 4985 (1978)
87%
Synthesis, 891 (1978)
ALCOHOLS FROM ALDEHYDES
SECTION 34
31
BH3 -SMe2
CH20H
Ph
82%
Ph
-
JOC 43, 1829 (1978)
C5H11-CHO
9 - BBN
a
py r id ine
*
CgH1 -CH20H
100%
-
JOC 42, 4169 (1977)
C6H1 3CH0
(HA1 N - i -Pr)6
*
CgH13CH20H
98%
Z Chem 17, 18 (1977)
Ph-CHO
MgH2
+
P h -CH20H
100%
JOC 43, 1557 (1978)
PhCH=CHCHO
H2 ,co _____I)
RhCl
PhCH=CH-CH20H
BCS Japan 50, 2148 (1977)
83 %
32
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
9-BBN
Ph-CHZCH-CHO
Ph-CH=CH-CH20H
SECTION 34
86%
JOC 42, 1197 (1977)
100%
Chem L e t t , 1085 (1977)
C6H1 3-CH0
H2
w
C6H13CH20H
88%
RuCl ( CO) 2L2
J Organometal Chem 145, 189 (1978)
R-CHO
IrH3L3,HOAc
*
R-CH20H
Ketones a r e n o t reduced.
J Organometal Chem 129, C43 (1977)
SECTION 34
ALCOHOLS
FROM ALDEHYDES
33
Aldehydes are s e l e c t i v e l y reduced i n t h e presence o f ketones by LiBH4 on molecular seives. JOC 44, 3969 (1979)
88%ee JACS
R-CDO
1 )3-pinanyl-9-BBN
*
2)HOCH2CH2NH2 R = a1 k y l , a r y l
99, 5211
(1977)
0"
RWC-D
I H
%80% 58-86%ee
,ally1 JACS 101, 2352 (1979)
Bu-CHo
BuMnI
acetone
*
Bu2CHOH
T e t r L e t t , 3383 (1977)
89%
34
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
O " \
'0
A1
/
SECTION 34
H
'OEt
H
Ph-CDO
75%
JACS
CH3CH2CH0
1 )CH2=CHCH2B(C4H9)2
2) triethanolamine
x,3129 (1979) +
CH3CH2
\iii OH
Bull Acad USSR Chem
R
= a1 kyl
82%ee
, Ph
27, 1663
(1 979)
Me
Angew Int Ed
3,306
(1979)
SECTION 34
35
ALCOHOLS FROM ALDEHYDES
B u 3 S n N
Ar-CHO
*
Ar
%go%
BF3*Et20, CH2C12
A r = Subst. P h , f u r y l , t h i o p h e n y l , e t c . Chem L e t t , 919 (1979)
cl,-x/Q
OH
2 BuLi
t
-i - P r C H O
47%
CH3
56%ee Chem L e t t , 219 (1978)
PhCHO t
Bu2Mg
>
Chem L e t t , 601 (1978)
Bu
94% 88%ee
36
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
Me8Sn3 ,hv
SECTION 36
b
benzene
59%
T e t r L e t t , 2847 (1978)
Related methods:
Section 35
Alcohols from Ketones (Section 42)
Alcohols and Phenols from A l k y l s , Methylenes and A r v l s
No examples o f t h e r e a c t i o n R R ' + ROH ( R ' = a l k y l , a r y l , e t c . ) occur i n t h e l i t e r a t u r e . For r e a c t i o n s o f t h e type RH +. ROH (R=alkyl o r a r y l ) see Section 41 (Alcohols and Phenols from Hydrides).
Section 36
0II
Alcohols from Amides
t-Bu-C-NMe2
L i Et3BH THF
+ t-BU-CH20H
Synthesis, 635 (1977)
95%
ALCOHOLS AND PHENOLS FROM AMINES
SECTION 37
1
NaBH4
*
-C-lMe NO glyme
PhCH20H
37
84%
JOC 44, 860 (1979)
S e c t i o n 37
A l c o h o l s and Phenols f r o m M i n e s
4 6
JCS P e r k i n I , 1114 (1977)
cu20
Cu
CH3
2 t ,H20
b
CH3
JOC 42, 2053 (1977)
93%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
38
Section 38
SECTION 38
Alcohols and Phenols from E s t e r s
-
OH
TH F
71%
JOC 42, 512 (1977)
BH~OP Ph-COOEt
7
PhCH20H
89%
JOC 42, 3963 (1977)
0
‘d- OMEM
P-OMEM
-
COOMEM
LiEt3BH
T e t r L e t t , 4705 (1979)
90%
SECTION 39
ALCOHOLS AND PHENOLS FROM ETHERS AND EPOXIDES
0 \I
Li
R-O-C-R'
*
ROH
39
7 1-97%
NH3
R ' = Ph o r t-Bu
JOC 44, 2810 (1979
fH20Ac
;H20Ac NaBH4
Q
O A bMe
c
87%
*
DME
OMe
Benzyl e s t e r s , benzoates, and cinnamates are unaffected. JOC
Related Methods:
Section 39
43,
155 (1978)
Carboxylic Acids from Esters - Section 23, P r o t e c t i o n o f Alcohols - Section 45A
Alcohols and Phenols from Ethers and Epoxides
6
Me3Si C1
NaI
*
6
JOC 44, 1247 (1979)
90%
40
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
C6Hl
-0Me
1 )Me3Si I
*
2 ) H20
‘sHl
SECTION 39
95%
1OH
JOC 42, 3761 (1977)
A1 Br3
98%
A1 Br3 EtSH
@OH
OH
78%
Chem L e t t , 97 (1979)
Ph-OMe
I2 ,PhSiMe3
*
Ph-OH
Synthesis, 417 (1977)
9 0%
SECTION 39
ALCOHOLS AND PHENOLS FROM ETHERS AND EPOXIDES
wcN OMe
41
OH
i
1
NaCN
~
79%
DMSO
T e t r L e t t , 5183 (1978)
Ar-OEt
BBr3
CH2C1
*
Ar-OH
64-91 %
Synth Corn 9, 407 (1979)
Jq
cycl ohexene Ph-CH2/
A1 C1 ,Pd/C
*
HO
cholestanol Synthesis, 825 (1978)
1 ) Me3SiC1, NaI Ph-O-CH2Ph 2 ) H20
*
PhOH t
PhCH21
JCS Chem Corn, 874 (1978)
81 %
42
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
qHl7 (rakN*
SECTION 39
electrochemical oxidation
95%
‘sHl 70H
MeCN/CH2C1
Me
Angew I n t Ed 17. 673 (1978)
Ar3@,
R-O-CH2Ph
CH3CN
X
Ar = B
NaHC03
e
*
ROH
X = Br or H
Angew I n t Ed 18, 801 and 802 ( 1 979)
A d d i t i o n a l examples of e t h e r cleavages may be found i n S e c t i o n 45A ( P r o t e c t i o n of A l c o h o l s and Phenols).
Can J Chem
56,
1177 (1978)
SECTION 39
ALCOHOLS AND PHENOLS FROM ETHERS AND EPBXIDES
BupCuLi
43
*
T e t r L e t t , 3407 (1977)
T e t r L e t t , 1503 (1979)
85% 10% C U I
T e t r L e t t , 4069 (1978)
44
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 40
Section 40 Alcohols and Phenols from Halides
>c/ Br
1)
Mg, THF
2) Moo5, pyr, HMPA
*
OH
70%
Also works with aromatic halides. Piust
J Chem
1 ) Mg, THF
Ph-Br
*
2) Moo4 , Pyr , HMPA
2, 2091 (1978) Ph-OH
89%
JOC 42, 1479 (1977)
1)
Bu-I
2)
40fllLi Arc I ~HCHC.,)
LiAlH4
OH BU-CHCH~
JOC 43, 4255 (1978)
3 8%
SECTION 40
45
ALCOHOLS AND PHENOLS FROM HALIDES
1 ) NaH, CH2(COSEt)2
*
BzCl 2 ) Raney N i
45%
BzCH2CH20H
Can J Chem 57, 2522 (1979)
PhCHO , E t 2 A 1 C1 -Zn
CH (OH) P h
CuBr, THF
100% JACS 99, 7705 (1977)
1 ) PhCH2MgC1 95%
2 1f i M g B r
3) H20 Et
T e t r L e t t , 51 79 (1978)
46
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1) 2)
Bu2CuLi Me1
*
SECTION 41
WMe 96%
JACS 99, 5816 (1977)
S e c t i o n 41
A l c o h o l s and Phenols f r o m Hydrides
-
Angew I n t Ed 18, 407 (1979)
Angew I n t Ed 18, 68 and 69 (1979) Review:
"Superacid-Catalyzed Oxygenation of A1 kanes" Angew I n t Ed
17,909
(1978)
SECTION 41
ALCOHOLS AND PHENOLS FROM HYDRIDES
47 64%
electrocatalysis Chem Ber
s,3561
(1977)
Synthesis, 215 (1978)
Benzeneseleneni c
OAc
OAc Chern Lett, 763 (1979)
48
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 42
1 ) LDA
2)
7n%
Moo5, Pyr, HMPA
k 4 M e
same conditions d
i
j
-
O
M
e
74%
JOC 43, 188 (1978)
Section 42
Alcohols from Ketones
COOMe CeCl CHO
NaBH4
*
OH
CHO
-
JACS 101, 5848 (1979)
75%
S E C T I O N 42
ALCOHOLS FROM KETONES
-a
49
PH
0
Na2S204 H20/di oxane
80%
Synthesis, 246 (1977)
dl
0
2 -pro pa no 1 +
alumina
HO
90%
JOC 42, 1202 (1977)
NaH, L-AmONa
90%
Ni ( O A C ) ~
J O C 43, 4804 (1978) T e t r L e t t , 1069 ( 1 977) OH
0
BH~OH~
-6 JOC 42, 3963 (1977)
86%
50
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
n-C6H1
0
II 3-C-Me
NaBH4,
SECTION 42
PH
A1203
g-C6H, 3-CH-Me
ether
90%
S y n t h e s i s , 891 (1978)
8
j?
(HA1 N - i -Pr)6
-6
95%
Z Chem 17, 18 (1977)
OH
90%
T e t r L e t t , 4985 (1978)
BugSnH
silica gel
HO
JOC 43, 3977 (1978)
89%
SECTION 42
ALCOHOLS FROM KETONES
51
(YCH3
tYCH3
H2, NaOH MeOH, [Rh ( B i py)2]@*
>go%
Can be accomplished i n t h e presence o f o l e f i n s . J Organometal Chem
157,
345(1978)
F H
98% H
-, 2664
BCS Japan 51
(1978)
MeMg0-2 ,6-l-Pr2C6H3
-
JOC 43, 4094 (1978)
89 %
52
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 42
H2' Rh
i-PrOH HC1, -
99%
CMe3
CMe3 Chem L e t t , 963 (1977)
H JOC 43, 1564 (1978)
76%
L i (HB-IPC-9-BBN) THF, -78'
99% JOC 42, 2534 (1977)
ALCOHOLS FROM KETONES
SECTION 42
53
99%ee JACS 101, 3129 (1979) JACS 101, - 5843 (1979)
0-H
0
H-
JOC 44, _-1363 (1979)
OH
54
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
II 0
LiA1H4
SECTION 42
OH I
*
97%
IAr
L
Heterocycles 12, 499 ( 1 979)
0
II
Ph-C-CH3
L i A1 H4
+
OH I Ph-CH-CH3
93%
(S) 92%ee
Chem L e t t , 783 (1977)
0 II P h- C- CH3
L i A1 H4'
H
CH2NHPh
*
H
93%
\*/OH
A\
Ph
CH3
92%ee BCS Japan 51, 1869 (1978)
SECTION 42
ALCOHOLS FROM KETONES
H OH \i Ph-C-CH3
0
II
*
Ph-C-CH3
THF
55
32%ee Chem Pharm B u l l
0 II CH3-C-COOEt
H2, CPPM-Rh
92%
*
27, 1479
(1979)
PH
+
CH3-CH-COOEt
99%
*
65%ee
CPPM =
ph2pb I
CH2PPh2
T e t r L e t t , 3735 (1977)
0
II
Ph/c'cooEt
Mg(C104)2, MeCN
-
c h i r a l 1,4-di h y d r o p y r i d i ne crown e t h e r
101,2759 JACs 101,7036 JACS
H
Ph'
(1979) (1979)
'COOEt 61% 86Xee
56
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
0
a - N p P h S i H2
It Me- C- COOPr
( - ) DIOP
*
OH
Me-LH-COOPr
SECTION 4 2
90%
*
85Xee
JOC 42, 1671 (1977)
4 0
-6 OH
9-BBN
JOC 42, 1197 ( 1 9 7 7 )
0
T e t r L e t t , 2369 (1977)
85%
SECTION 42
ALCOHOLS FROM KETONES
57
NaBH4
100%
CeCl 100, 2226 (1978) JACS -
The c a t a l y s t Rh( bipy)2 8 s e l e c t i v e l y hydrogenates ketones t o alcohols i n the presence of o l e f i n s .
J Organometal Chem
8 Me-C- COOH
1 1 (Et0)3P 2) NaOH
*
140,63
OH I Me-CH-COOH
(1977)
94%
JOC 42, 2797 (1977)
Et2C=0
BuMnI acetone
+
BU ( E t ) 2 C - O H
Tetr Lett, 3383 (1977)
86 %
58
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 43
81 %
2) H30t
JACS 99. 5317 (1977) >
A
-
electroreduction ~
-
98%
MeOH/d ioxane JACS 100, 545 (1978)
Review: " S t e r e o c h e m i s t r y and Mechanismof Ketone Reductions by H y d r i d e Reagents" Tetrahedron 35, 449 (1979)
Related methods: A l c o h o l s f r o m Aldehydes ( S e c t i o n 34)
S e c t i o n 43
A1 coho1 s and Phenol s from. N i t r i l es
No a d d i t i o n a l examples
ALCOHOLS FROM OLEFINS
SECTION 44
-
Section 44
59
Alcohols from O l e f i n s
For t he prepara ti o n o f d i o l s f r o m o l e f i n s see Section 323 (A1 cohol -A1 cohol )
1 ) C l B H i SMe2
2 ) H202, NaOH
99% OH
JOC 42, 2533 (1977)
JCS Chem Corn, 796 (1979)
M
1 ) D i isopi nocamphyl borane
2) H202, %H
72% 98%ee
Israel J Chem 15, 12 (1977)
60
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 44
Ph
"'y \
H2
ph+ Et
CH3
(-) DIOP-PtC12,SnCl~
90%
Et 37%ee
I s r a e l J Chem
1) LiEt3BH 2 ) CH3S03H Ph -CH=CH2
3) NaOH, H202
*
3,221
(1977)
90%
Ph-CH-CH3 dH
JOC 42, 1482 (1977)
A1 H4 ,Cp2Ti (A1 H3)2 1. 2. 02,HC1 CH= CH2
*
Q-
CH2CH20H
Chem L e t t , 1 1 1 7 ( 1 9 7 7 )
86%
SECTION 44
ALCOHOLS FROM OLEFINS
(aB
61
1 ) LiA1H(OMe)3, COY THF
86%
2 ) HC1
3 ) H202,NaOH
S y n t h e s i s , 676 (1978)
1 ) hv y
B
@
)
2
2, CH3C02H 3) NaOH, H202
*yp 69%
JACS 99, 5192 (1977)
t
85%
T e t r L e t t , 1895 (1979)
62
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 44
96%
JCS Perkin I . 1172 (1977)
30%
-
Comptes Rendus 289, 227 (1979)
1 ) CH3MgI 2 ) CH3CH0
* A
61 %
CHOH
r
CH3
B u l l Acad USSR Chem
27,
1364 ( 1 979)
Section 45A
PROTECTION OF ALCOHOLS AND PHENOLS
63
A1 cohol s from M i scel 1aneous Compounds
Section 45
No a d d i t i o n a l examples
For conversions o f boranes t o alcohols, see Section 44
Section 45A
R-OH
Protection
o f Alcohols and Phenols
TsOH*p y r i d i ne
*
R-0
This c a t a l y s t i s m i l d e r than most others, and i s u s e f u l w i t h a c i d - s e n s i t i ve a1cohol s
.
JOC 42, 3772 (1977)
b , Amberlyst
R-OH
H-15
CH30H
( Y O R
Amberlyst H-15
Synthesis, 618 (1979)
> 90%
64
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
R-OH
SECTION 4 5 A
q-J 7 0-CCH2 Ph
\/ o r MeOH
Rec T r a v C h i m 98, 371 (1979)
R-0-THP
a c i d - w a s h e d Dowex r e s i n MeOH Synth
+
R-OH
Corn 9, 271 (1979)
JOC 43, 3548 (1978)
>97%
SECTION 45A
PROTECTION
+
OF ALCOHOLS AND PHENOLS
Can J Chem
55,
CH20Ac
OMe
65
3351 (1977)
CH20Ac NaBH4
OAc
DME
87%
*
$OH
OMe
Benzyl e s t e r s , benzoates, and cinnamates are unaffected. JOC 43, 155 (1978)
1) AgC104, c o l l i d i n e 2) morphol i n e
R-O-!*
R-OH
Br2CH
JCS Chem Comm, 987 (1979)
66
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
10% Pd/C
cycl ohexene or NaH2P02
0
*
SECTION 45A
R-OH
Tetr Lett, 555 (1979)
c1 -c-0
R-OH
\
0
!-
R- 0- 0-
H 2 0, dioxane Tetr Lett, 1571 (1977)
Boc-Val-Tyr(Bzl).OMe
Me3Si I
Boc-Val -Tyr.OMe
JCS Chem Comm, 495 (1979)
%I100%
SECTION 4 5 A
PROTECTION OF ALCOHOLS AND PHENOLS
67
Me3COCH C1, E t 3 N
R-OH
Me3COCH20R
TFA, H20
-
JOC 4 3 , 3964 (1978)
R-OH
Me2S0 t Me S i c 1
+
R-O-CH2-O-R
-
JOC 44, 3727 (1979)
1 ) BrZnCH2COOEt Ph-OH
*
PhOCH20CH3
2) C H * ( 0 W 2 S y n t h e s i s , 567 (1977)
72%
68
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 4 5 A
CH2C1 2, C1 CH20Me Ar-OH
b
H20, NaOH, A d o g e n 464
Ar-OCH20Me
79-95%
T e t r L e t t , 661 (1978)
S y n t h Comm
9, 57
(1979)
1 DMSO, A c 2 0
R-OH
acetone
A u s t J Chem
2, 1031
(1978)
SECTION 45A
PROTECTION OF ALCOHOLS AND PHENOLS C1 CH2SCH3, AgN03
69
* R-OCH2SCH3
R-OH
Et3N, benzene Chem L e t t , 1277 (1979)
1) NaOH 2) MeSCH2C1, HMPA
Ar-OH
Ar-OCH2SCH3
T e t r L e t t , 533 (1977)
Me
\a3
R-OH
Me-<:]
FS02@
Me I R-O-CHS ( C H Z ) ~ S M ~
60% Synth Comm 9 , 107 (1979)
70
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
ROSi (Me)2-1-6u
Aq. HF
*
CH3CN
SECTION 45A
R-OH
Tetr Lett, 3981 (1979)
R-OH
R-OH
Me3SiC1, L i 2 S MeCN
t-BuMe2Si C1 Li2S, MeCN
*
R-OSiMe3
*
R-OSiMep-t-Bu JOC
44,
4272 (1979)
Use of triethylsilyl ethers as -OH protecting groups i n t h e synthesis of prostaglandin D,.
JCS Chem Comm, 156 (1979)
R-0-Si Me2-t-Bu -
BF3*Et20
*
R-OH
Used with prostaglandin intermediates. Synth Corn
9, 295
(1979)
SECTION 45A
PROTECTION OF ALCOHOLS AND PHENOLS
Use o f p o l y s t y r y l b o r o n i c a c i d t o p r o t e c t cis-1, 3 - d i o l s i n glycosides.
acetone, H20
JACS
101,432
(1979)
-
I s r a e l J Chem 17, 253 (1978)
Review:
"Carbohydrate C y c l i c Acetal Formation and M i g r a t i o n "
-
Chem Rev 79, 491 (1979)
71
72
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 45A
JCS Chem Comm, 639 (1978)
Re1ated methods : Ethers from Alcohols Alcohols from Ethers Esters from Alcohols Alcohols from Esters
-
-
-
Sectiorl 123 Section 39 Section 108 Section
38
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 4
PREPARATION OF ALDEHYDES Secti 01 46
A1 dehydes from Acetylenes
No add tional examples
Section 47
Aldehydes from Carboxylic Acids and Acid Halides DIBAH -CgH19-CH0
72%
-6
JCS Chem Comm, 330 (1978)
2) 1 ) pyridinium Me2S :BH3 chlorochromate
Synthesis, 704 (1979) 73
69%
74
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S
X-(CH2)nCOOH
U -X-(CH2),-C-N
DIBAH
LI t o 1 uene
Et?N
-
X-(CH2),-CH0 %70-90%
X = Ph, CN, B r
Q
&, -
1
HN
SECTION 47
B u l l Chem SOC Japan 52, 555 (1979)
CH2COOH
1 ) e l e c t r o l y s i s , DMSO
* 2 ) NaHC03
OMe
b;
72%
OMe JOC 42, 1461 (1977)
C H 3 W 2 15 -CH-COOH I
SPh
electrol sjs CH3(CH2 )5CH(OMe)2
*
93%
MeOH,LiC104 T e t r L e t t , 1045 (1979)
C7H15-CH2COOH
+ *C
'Aq!s:
+C7H1 5CH0
7H 15 -CH
N-N
T e t r L e t t , 381 (1977)
56%
SECTION 47
ALDEHYDES FROM CARBOXYLIC ACIDS AND A C I D HALIDES
NaBH4, CdC12
0 It C8H1 7-C-C1
*
75
56%
C8H17CH0
DMF
JCS Chem Corn, 354 (1978)
0II
w c-cl
3 NMe4* HFe ( C0)4 CHo-*
6
99%
T e t r L e t t , 781 (1977)
( Ph3P)2CuBH4
* Ph3P, acetone c1
80%
c1
T e t r L e t t , 1437 and 2473 (1978)
0 II CH3(CH2)8C-C1
( Ph3P ) 2CuBH4
*
CH3(CH2)8CH0
PPh3, acetone
T e t r L e t t , 975 (1979)
79%
76
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 48
SECTION 48
Aldehvdes from Alcohols
CH3-( CH2)9-CH20H
DMSO, (COCl )2
Et3N
*
CH3( CH2)9-CH0
99%
Synthesis, 297 (1978) Tetrahedron 34, 1651 (1 978)
JOC DMSO, TFAA
43,
*
p C H 2 0 H
2480 (1978)
P C H O
78%
R3N, CH2C12 Synthesis, 297 (1978) Me2S0 , (COCl )2
*
F C H O
98%
Et3N
JOC
-
44,
4148 (1979)
DMS-NCS
CH3(CH2)8CH20H
CH3(CH2)8CH0
t o 1 uene
-
Tetrahedron 34, 1651 (1 978)
94%
SECTION
ALDEHYDES FROM ALCOHOLS
48
77
1 ) PrMgBr
wCH20H
2 ) t-BuOMgBr,
*
-CHO
80%
NCS
BCS Japan 50, 2773 (1977)
*
O-( C H ~ ) ~ C H ~ K2Cr04 OH , H2S04/H20 Q CHCl 3 , Bu4NHS04
83%
0-(CH2) 7-CH0
S y n t h e s i s , 134 (1979) Na2Cr207, H2S04 '1 5H31CH20H
Bu4NHS04, CH2C1
C15H31CH0
90%
JCS P e r k i n 11, 788 (1979)
0 0
Ph
- 2
CH OH
Bu4NHCr04 p h w C H o CHCl
S y n t h e s i s , 356 (1979)
91 %
78
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
K2Cr207 9 H2S04
P hCH2CH20H
*
SECTION 48
PhCH2CH0
90%
CH2C12, Bu4NHS04
T e t r L e t t , 1601 (1978)
Ph - 2
CH OH
K2Cr207, benzene
CHo
Ph
91%
phase-transfer c a t . T e t r L e t t , 4167 (1977) p y r i d i n i u m dichromate
R-CHiOH
*
R-CHO
70-98%
CH2C1
T e t r L e t t , 399 (1979)
FHO
p y r id i n i um chromate s i l i c a gel
-8
Tetrahadron 35, 1789 (1 979)
80%
SECTION 48
ALDEHYDES FROM ALCOHOLS
H2Cr04/Si02
n-C9H1 9-CH20H
*
CgH19-CH0
79
86%
Synthesis, 534 (1978) Cr03/cel i t e
P h- CH20H
-
E t20/ CH2C1
*
Ph-CHO
75%
Synthesis , 815 (1979)
CH20H
Cr03
*
-CHO
pol y ( v i n y l p y r i d i ne) r e s i n JOC
43,
91%
2618 (1978)
NiBr2
92%
-
JOC 44, 2955 (1979)
FeCl
Me2CH-CH20H
Me$H-CHO
hv
JOC 42, 171 (1977)
70%
80
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
CUCl,
SECTION 48
o2
PhCH20H K2C03, phenanthrol i n e
b
PhCHO
86%
T e t r L e t t , 1215 (1977)
T e t r L e t t , 839 (1978)
(PhjBiC1 )20
N
CH20H
CHo
Ph
Ph
JCS Chem Corn,
C:yBre Ph-CH20H
*
099 (1978)
Ph-CHO
Synthesis, 936
83%
90%
1978)
SECTION 48
ALDEHYDES
CH3( CH2)8CH20H
FROM ALCOHOLS
*
-t -BUOOH
81
CH3(CH2)8CH0
92%
T e t r L e t t , 2801 (1979)
P,
( PhSe)20 Ph-CH20H
+ Ph-CHO
99%
JCS Chem Corn, 952 (1978)
1.70%
JCS Perkin I , 1483 (
CH20H
DMSO
78
85%
ph+ CHO
Chem L e t t , 369 (1978) Related methods:
Ketones from Alcohols and Phenols (Section 168)
82
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 49
SECTION 49
Aldehvdes f r o m Aldehydes
Conjugate r e d u c t i o n s and Michael a1 k y l a t i o n s of c o n j u g a t e d aldehydes a r e l i s t e d i n S e c t i o n 74 ( A l k y l s from O l e f i n s ) .
BzBr, NaOH
*
Me2CH -CHO
Me C-CHO 21
t-Bu4NI
6
60%
BZ
Chem and I n d , 731 (1978) 1 ) KH, THF 96%
*
Br
O
H
C
P
T e t r L e t t , 491 (1978)
Li I 1 ) TMS-CHOMe
*
P
C
"
2) HCOOH
JCS Chem Comm, 822 (1979)
0 >90%
SECTION 50
ALDEHYDES FROM ALKYLS
a3
Review: "Synthesis o f Aldehydes, Ketones, and Carboxyl i c Acids from Lower Carbonyl Compounds by C-C Coup1 i n g Reactions".
Synthesis, 633 (1979)
Related Methods: Aldehydes from Ketones (Section 57), Ketones from Ketones (Section 177). A l s o v i a : O l e f i n i c aldehydes (Section 341).
Section 50
Aldehydes from Alk.yls
T e t r L e t t , 3331 (1979)
& Me
OMe
Ph
2) 1) 02/NBS, DDQ hv
~
f!@ Me0
OMe
Synthesis, 144 (1979)
68%
SECTION 52
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
84
S e c t i o n 51
PI
Aldehydes from Amides
LiA1H2( OCH2CH20Me)2
*
R-C-NMe2
R-CHO
41 -98%
toluene R = long-chain a l k y l
JOC (USSR)
13,1081
(1977)
82%
0 T e t r L e t t , 3875 (1979) S e c t i o n 52
Aldehydes from Amines
1 ) L-BuOCl
CH3(CH2)4-NH-(CH2)4CH3
CH3(CH2)3CH0
3) H3
+
JOC 43, 1467 (1978)
ALDEHYDES FROM AMINES
SECTION 52
85
Ph
@
Ph-CH2NH2
*
Ph
Ph-CHO
%45%
A
3)
JCS Perkin I , 2500 (1979) Ph
Ph
*
R- CH NH
R-CHO
2) (NCOOEt)2 3 ) H3$
R = alkyl , aryl
Tetr Lett, 2131 (1978)
2.70%
86
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 53
BZdehvdes f r o m F s t e r s H2OY A
Cl I Ph-CH2CHOAc
*
JOC (USSR) Section 54
SECTION 54
PhCH2CH0
14,254
91 %
(1978)
Aldehydes from E t h e r s
Ph - CH2 OMe
1) UF6 2)
Hp
Ph-CHO
78%
JACS 100, 5396 (1978)
1 ) N02BF4 PhCH20Me 2)
Hp
* Ph-CHO
JOC 42, 3097 (1977)
89%
ALDEHYDES FROM HALIDES
SECTION 55
a7
( PPh)3RuC12 A
JOC 42, 3360 (1977)
S e c t i o n 55
Aldeh.ydes from Hal i d e s
PhCH2Br
( B u ~ N2Cr207 )
*
PhCHO
95%
CHCl
Chem & I n d , 213 (1979)
Ph
0
I
ONa n-C H -CH2Br - 6 13
2)
*
C6HI3-CHO
A
JCS P e r k i n I , 2493 (1979)
60%
88
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 55
CHO 76%
2 ) NCS
Synth Corn
5, 575
*
Ph-CH2Br
(1976)
Ph-CHO
46%
2 ) hv, benzene
Synthesis, 619 (1978)
0
polymer-bound FeH( CO)4 FhCH2CH2Sr
*
PhCH2CH2CH0
JOC 43, 1598 (1978)
80%
ALDEHYDES FROM HALIDES
SECTION 55
P hCH2CH2MgBr
cHo *
PhCH2CH2CH0
89
75%
S y n t h e s i s , 403 (1978)
1 ) Et2NCH2CN, LDA
H20, THF
T e t r L e t t , 5175 (1978)
8
Me-S-CH2SMe PhMgBr
-
* Ph-CH (SMe)2
66%
TH F T e t r L e t t , 3883 (1977)
1 Ph-C-CH2Br
Et2NOH
0 I1 Ph-C-CHO
JOC 42, 754 (1977)
78%
90
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 57
Section 56
2) NaOMe 100, 7600 (1978) JACS Section 57
Aldehydes from Ketones
Li I
1 )TMS-CHOMe
2) HCOOH
JCS Chem Comm, 822 (3979)
>go%
SECTION 57
Q
ALDEHYDES FROM KETONES
Li I 1) C1CHSiMe3
*
2) BF3*Et20 MeOH JACS
99, 4536
6
91
95%
(1977)
0 II 1 ) (BuO) PCHOTHP 2 1 Li %80%
3 ) H30+ T e t r L e t t , 3629 (1978)
JOC
44,
4847 (1979)
COMPENDIUM OF O R G A N I C SYNTHETIC METHODS VOL 4
92
SECTION 59
/
80%
JOC 43, 3792 (1978)
S e c t i o n 58
Aldehydes f r o m N i t r i l e s
No a d d i t i o n a l examples
S e c t i o n 59
Aldehydes from O l e f i n s
Ru04 ( c a t .
Br Br
NaI04, NaHC03
*
Br
FHO 79%
Br
A c t a Chem Scand B32, 693 (1978)
SECTION
ALDEHYDES FROM OLEFINS
59
a
1 ) K (i-PrO)3BH
93
-6
0 ,CO
2) H202
92%
Synthesis, 701 (1979)
1) PhSH, AIBN, hv
2 ) NCS
* C-HO
40%
3) HgC12, CdC03
Synth Corn
6, 575
(1976)
C
H
1 ) LiA1H4, TiC14
*W
M 2)
orH 0
Chem Lett, 1 6 7 ( 1 9 7 9 )
O
45%
94
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 60
SECTION 60
Aldehydes from Miscellaneous Compounds
CrCl
Et-CH2-N02
66%
Et-CHO
CH30H
Synthesis, 792 (1977) 1) NaOH, MeOH
*
CH3 ( CH2) 6CH0
67%
JOC 43, 1271 (1978)
Na2S H-!=CH-t-Bu -
8
*
H-C-CH
MeOH, E t 3 N
-t-Bu 2 -
90%
JOC 44, 4712 (1979)
R n-C7H, 5-CH2-S-Ph
1 ) TFAA
*
C7H15-CH0
2) HgC12, MeCN/H20 Synthesis , 881 (1978)
86%
SECTION 60A
Section 60A
PROTECTION OF ALDEHYDES
95
P r o t e c t i o n o f Aldehydes HC(OMe)3, MeOH
R-CHO
~
/OMe
Meo\ R- C-H
LnCl Ln = any of several lanthamides Ketones remain unaffected under these r e a c t i o n conditions.
JOC 44, 4187 (1979) Ph
Me\
HC ( OMe )
MHO*
O , Me w “H
Ph
montmori 11o n i t e
92%
Synthesis, 467 (1977)
fi
C5HiiC-~
HC ( OMe )
MeOH, ErC13
+
96% MeoYoMe
/\
‘gHll
H
JCS Chem Comm, 976 (1978)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
96
/“\
/OMe
Me3Si I
*
ti
‘gH1 7
SECTION 60A
C5H11-CH0
85%
C H C l g/propene
T e t r L e t t , 4175 (1977)
HOCH2-A-CH20H, DMF R-CHO
*
Me2S04 A = -CH CH - o r -CH=CH2 2 S y n t h e s i s , 975 (1979)
jr”’
dCHO dH/O r 0
Me C ( CH2 0H )
70%
7
TsOH, benzene
H
NI
H
S y n t h e s i s , 295 (1 978)
SECTION 60A
PROTECTION OF ALDEHYDES
97
A d i v i n y l benzene-styrene copolymer c o n t a i n i n g 1 , 3 - d i o l can s e r v e as a monoblocking agent for d i a l d e h y d e s :
groups
OHC, R
Can J Chem
MeSSMe R-CHO
____)
Bu3P
MeS
\
/SMe
R /c\
H
54, 3824
(1976)
Chem L e t t , 767 (1979)
E t S H , C1SiMe3
Ph-CHO
CHCl
95%
Ph-f(SEt)2
H Synth Comm
7,
283 (1977)
98
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
EtS-SiMe3
CH3( CH2)4CH0
SECTION 60A
OTMS 82%
EtS\C/
/H ‘
CH3( CH* 14
JACS 99, 5009 (1977)
electrochemical oxidation
*
PH-CHO
77%
MeCN/H20, NaCl O4
JCS Chem Corn, 255 (1978)
CHO
88 % MeOH/THF
I N02 Chem P h a m 26, 3743 (1978)
PROTECTION OF ALDEHYDES
SECTION 60A
n
99
1 ) Me2S*Br2
Ph-CHO
w
75%
2) H20
Synthesis, 720 (1979)
n
1 ) Et30BF4
R
2) H20
8 0
sxs=o H
*
R-CHO
R = a l k y l , subst. Ph
Angew I n t Ed 18, 165 (1979)
H20*’ R-CH=N-NHTS
59
MeOH/di oxane
*
R-CHO
Synthesis, 919 (1978)
%75%
100
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
rHTs R
NaN02 , CF3COOH
H
*
SECTION 60A
R-CHO
Synthesis, 207 (1979)
NNTs
II
R
A
T l (OAc)
R-CHO
H
HOAc
T e t r L e t t , 4583 (1979)
INHTs R
H
CuS04, H20
90%
+
MeOH, THF
R
/"\H
Gazz Chim I t a l
P h -CH=NNH TOS
Br2, CH2C12
*
708,
137 (1978)
Ph-CHO
NaHC03, H20/HMPT
Synthesis, 113 (1979)
74%
SECTION 60A
PROTECTION OF ALDEHYDES
02’ hv
* -n-C1 1H23-CH0
methyl ene bl ue
101
52%
Synthesis, 893 (1977) benzeneselenenic anh y d r i de
* C10H21CH0
C1 OH2, -CH( SeMe)2
84%
Synthesis , 877 (1 979)
-
See Section 367 (Ether O l e f i n ) f o r t h e formation o f enol e t h e r s . Many o f t h e methods i n S e c ti o n 180A ( P r o t e c t i o n o f Ketones) are a7so a p p l i c a b l e t o aldehydes,
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 5
PREPARATION OF ALWLS, METHYLENES, AND ARYLS T h i s c h a p t e r l i s t s t h e c o n v e r s i o n o f f u n c t i o n a l groups i n t o Me, Et CH2, Ph, e t c .
...,
S e c t i o n 61
A1 k y l s, Methyl enes, and Aryl s from Acetylenes t-BuONa NaH, -
CH 3C=C-C3H7 -
* CH3-CH2-CH2-C3H7
FeC13, THF
95%
T e t r L e t t , 3947 (1977)
Me
Ph-0-CH-CsCMgBr I
62%
2
CH2=CH-CH2-ZnBr
Synthes s , 838 1978) 102
SECTION 62
ALKYLS FROM CARBOXYLIC ACIDS
103
TMS
JACS 99, 4058 (1977)
Review: "Transition i n Organic Synthesis"
-
Metal
-
Catalyzed Acetylene Cycl i z a t i o n s
Accounts Chem Res 10, 1 (1977)
Review: " T r a n s i t i o n Metal Catalyzed Acetylene Cool igornerzations f o r t h e Synthesis o f Complex M o l e c u l e s ~ ~ Strem Chemiker ,V-I Section 62
#2, 1 (1978)
A l k y l s from Carboxylic Acids
C9H19-CH3
CgH1 9COOH
2 ) NaBH4 3) Na, NH3
JCS Perkin I,1133 (1978)
%80%
104
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
COOH
SECTION 63
1) C1CO2EtY Et N
2 ) NaiH,
aOH
OH
Chem Pharm B u l l
S e c t i o n 63
27,
816 (1979)
A l k y l s from - 1coho1 s
Reactions i n which h y d r o x y l groups a r e r e p l a c e d by a l k y l , e.g. ROH + RMe, a r e i n c l u d e d i n t h i s s e c t i o n . F o r t h e c o n v e r s i o n ROH 4 RH see S e c t i o n 153 (Hydrides f r o m A l c o h o l s and Phenols)
0
II
C5H11 -C-NHCHZOH
A1 E t 3
0
II
C5H1 1-C-NHCH2Et
benzene
T e t r L e t t , 1465 (1977)
T e t r L e t t , 3n03 (1977)
71 %
SECTION 64
Section 64
105
ALKY LS FROM ALDEHYDES
A l k y l s f r o m Aldehydes
PhCH2CH0
PhCH2CH3 2 ) Nay NH3
4
%70%
JCS P e r k i n I, 1133 (1978)
E t 3 S i H , BF3
*
CH2C1 OMe
100%
OMe
JOC 43, 374 (1978)
c y c l ohexene Ph- CH ( OMe)
*
Ph-CH3
A1C13, Pd/C
Synthesis, 825 (1978)
80%
106
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 67
t-BuLi PhCH2CH2CH=NNHTS -Ph(
CH2)3-L-B~
61%
TH F T e t r L e t t , 135 (1977)
Related methods: Also v i a :
Section 65
A1 k y l s and Methylenes from Ketones (Section 72)
V i n y l Ethers (Section 69)
A l k y l s and A r y l s from A l k y l s and A r y l s
No a d d i t i o n a l examples
Section 66
A l k y l s from Amides
Me2CuLi
Ph-CH,-N(Tf)2
Ph-CH2CH3
T e t r L e t t , 4727 (1978)
Section 67
A l k y l s . Methylenes, and A r y l s from Amines
No a d d i t i o n a l examples
60%
ALKYLS AND ARYLS FROM ETHERS
Section 69
Section 68
107
A l k y l s from Esters 1 ) Me3SiI/12
*
Ph-COOMe
2) H S i C13-Pr3N
3)
Ph-CH3
68%
MeCN
0
OH JOC
6””‘
44,
iPh
2185 (1979)
b”” SPh
Bu2CuLi
89%
-
JACS 101, 4413 (1979)
Section 69
A l k y l s and A r y l s from Ethers
The conversion ROR section.
-+
R R ’ ( R ’ = a l k y l , a r y l ) i s included i n t h i s
7 5%
PhMgBr
JACS
c. 2246 (1979)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
108
PhCH2CH2MgBr OCH2 CH= CHPr
*
SECTION 69
Ph(CH2).$H=CHPr
94%
MgBr2, THF
Chem L e t t , 689 (1978)
1 ) BuLi
$Me
91 %
OMe OMe
43, 1 3 7 2 ( 1 9 7 8 ) JOC -
C-
CH3MgBr
Me S
6H 13
N i L2C1
7 1%
‘gH1 3
JCS Chem Comm, 637 (1979)
SECTION 70
ALKYLS AND ARYLS FROM HALIDES AND SULFONATES
PhMgBr
*
PhS\=/Ph
109
Ph
WPh 97%
N i C12( PPh3)2
-
S e c t i o n 70
T e t r L e t t , 43 (1979)
A l k y l s and A r y l s from Halides and Sulfonates
The replacement o f halogen by a l k y l o r a r y l Groups i s i n c l u d e d i n t h i s s e c t i o n . For t h e conversion RX + RH (X=halo) see Section 160 (Hydrides from Halides and Sulfonates). Ts
n-C H MgBr 6 13
100%
b
10% C U ( A C A C ) ~ T e t r L e t t , 2393 (1979)
1) BuLi 2) Et3B
b
3 ) 12
JOC 43, 1279 (1978)
61 %
110
COMPENOIUM
OF ORGANIC SYNTHETIC METHODS VOL 4 Me4Sn
*
P h CH2B r
SECTION 70
PhCH2CH3
70%
Pd c a t a l y s t HMPA 101 , 4992 (1979) JACS SnBu3 100% (Ph3P I 4Pd
6
Chem L e t t , 301 (1977)
*
PhZnCl
OMe
87%
OMe
JOC 42, 1821 (1977)
VC1 3/LiA1 H4 2Ph2CHBr
b
Ph2CH-CHPh2
THF Synthesis, 170 (1977)
95%
SECTION 70
ALKYLS AND ARYLS FROM HALIDES AND SULFONATES
111
Zn, HMPA 2 Ar-I
%go%
Ar-Ar NiBr2-Zn
A r = subst. Ph
Chem L e t t , 917 (1979)
-
t
Me3C-N
0
CsH, 7-CMe3
ether
0
90%
I
‘CHPh
-
JACS 101, 1044 (1979)
7 5
B
1 ) BuLi , Et20/HMPA
r
2 ) C-CsHllI 3) (COOH)2,
‘gH1 1 H20
T e t r L e t t , 4661 (1978)
69%
112
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 70
BuCH, Bu2Cu L i
*
\e>.O
41%
T e t r L e t t , 423 (1977)
L i 2[ PhSCu ( CH2)4CuPhS] 60%
T e t r L e t t , 1245 (1977)
BuLi
Bu
T e t r L e t t , 223 (1978)
92%
SECTION 71
P
h
ALKYLS AND ARYLS FROM HYDRIDES
m
113
MeCu*BBu3
CH B r
Me
85%
JACS 99, 8068 (1977)
S e c t i o n 71
A l k y l s and A r y l s f r o m Hydrides
T h i s s e c t i o n l i s t s examp a1 k y l o r a r y l ) For t h e see S e c t i o n 209 ( O l e f i n s and e s t e r s , see S e c t i o n (Esters from Esters).
.
es o f t h e r e a c t i o n RH -+ RR' (R, R ' = r e a c t i o n C=CH + C=CR (R = a l k y l o r a r y l ) from O l e f i n s ) . For a1 k y l a t i o n s o f ketones 77 (Ketones f r o m Ketones) and S e c t i o n 113
PhBr, Ph3P PhS-CH=CHMe
Ph I + PhS-CH=C-Me
Pd (OAc ) TMEDA/MeCN
JACS 101, 4743 (1979)
65%
114
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 71
ClG ’ )
Me&
67%
2) E t 3 N 3) RaNi
-
JACS 100, 7611 (1978)
*&
1 ) BzSPh, Me3COC1 2 ) NaOMe c1
3 ) LiA1H4
CH2Ph 77%
c1
JACS
100,7600
(1978)
C o l l Czech Chem Corn 43, 2174 (1978)
SECTION 72
ALKYLS, METHYLENES, AND ARYLS FROM KETONES
115
TFA
-
A u s t r a l i a n J Chem 32, 1531 (1979)
S e c t i o n 72
A l k y l s . Methulenes. and A w l s f r o m Ketones
The conversions R2C0 t h i s section,
+
RR, R2CH2, R2CHR’,
*
0
II
AC\
‘sHl 7
etc. are l i s t e d i n
CaHi7CH2CH3
%go%
2 ) Na, NH3
CH3
4 0
JCS P e r k i n I , 1133 (1978)
1 ) TsNHNH2
*
64%
2) c a t e c h o l borane , MeOH , Bu4NOAc Synth Comn
9,
275 (1979)
116
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 7 2
-0
E t 3 S i H , BF3 CH2C1
JOC
9, 374
(1978)
ph/cn 8
90%
NaBH4
CF3COOH
*
P h'cH2QBr
Br
94%
S y n t h e s i s , 763 (1978)
1 ) C1C02Et, E t 3 N Me0
2 ) NaBH4, H20
Me0
Chem P h a r m B u l l
27,
1490 ( 1 9 7 9 )
SECTION 72
ALKYLS, METHYLENES, AND ARYLS FROM KETONES
0
117
SePh JCS Chem Comm, 41 (1978)
CH2CH2CN
U
NaBH4
mCH2 U
w
CH3COOH NNHTs
@
NaBH4
CH3COOH
JOC 43, 2299 (1978)
adamant a n e t h i one
70%
KOH
adamantane
JOC 42, 3522 (1977)
72%
118
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
2) HC1
0
SECTION 72
H20
Synth Comm 7, 161 (1977)
Related methods:
A1 k y l s from Aldehydes (Section 64)
Also v i a v i n y l e th e rs (Section 69)
Section 73
A l k y l s , Methylenes and A r y l s from N i t r i l e s
No a d d i t i o n a l examples
Section 74
A l k y l s , Methylenes and A r y l s from O l e f i n s
The f o l l o w i n g r e a c t i o n types are i n c l u d e d i n t h i s s e c t i o n :
A.
B.
Hydrogenation o f o l e f i n s (and a r y l s ) . Dehydrogenations t o form a r y l s .
C.
A l k y l a t i o n s and a r y l a t i o n s o f o l e f i n s .
D.
Conjugate re d u c ti o n s o f conjugated aldehydes acids
ketones
e s t e r s and n i tri 1es.
E.
Conjugate a l k y l a t i o n s .
F.
Cyclopropanations , i n c l u d i n g h a l o c y c l opropanations
.
HYDROGENATION OF OLEFINS
SECTION 74A
74A:
0
119
Hydrogenation o f o l e f i n s (and a r y l s )
NaH, t-BuONa
*
N i ( O A C ) ,~ PhOCH3
0
95%
T e t r L e t t , 1069 (1977)
0
NaH, t-BuONa
0
*
FeC13, THF
80%
T e t r L e t t , 3947 (1977) LiA1H4
*
100%
COCl
JOC
43,
L i A1 H4-CoC1 &
0
2567 (1978)
T e t r L e t t , 4481 (1977)
96%
-
120
-
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1 ) LiA1H4, TiC14 2) H20
SECTION 74A
96%
-
J Organometal Chem 142, 71 (1977)
T e t r L e t t , 4579 (1977)
H2 s i l i c a - s u p p o r t e d L3RhC1
-0
(Higher r a t e s than f o r t h e homogeneous r e a c t i o n . )
JCS Chem Comm, 510 (1977)
Use of [Ir(COD)L(py)]PF6 and [Ir(COD)L2]PF6 as a c t i v e hydrogenation c a t a l y s t s f o r o l e f i n s .
J Organometal
141,205
(1977)
Ir(CO)C1L2 catalyzes t h e hydrogenation o f cyclopentene, styrene, and e t h y l a c r y l a t e a t 10 atm.
-
J . Organometal 129, 331 (1977)
SECTION 74A
HYDROGENATION OF OLEFINS
H2, NaH, Ni(OAc)2
*
121
r
9
8
%
THF/ EtOH T e t r L e t t , 3955 (1977)
-CH20H Ph
polymer-bound PdCL2 JOC
Q
P h &CH20H
H2
43,
H p , THF
100%
4686 (1978)
*
Q
90%
( p o l y s tyryl b i p y r i d i ne) palladium (0) I s r a e l J Chem
17,269
NaBH4, Co(I1)
JOC 44, 1014 (1979)
(1978)
79%
122
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 74A
100%
Tetr Lett, 3727 (1977)
aMe Me
H
pyr i d ine
H
-
Chem Pharm 26, 108 (1978)
hydrogenation.
Gives 60%ee w i t h a-ethylstyrene. Tetr Lett, 295 (1977)
H2, LiA1H4
*
s a1 icyl a1 dehyde- N i Tetr Lett, 2531 (1977)
80%
SECTION 74A
HYDROGENATION OF OLEFINS
H2(1 atm)
123
-0
polymer-bound Rh( I ) complex
T e t r L e t t , 3703 (1977)
95%
97%
T e t r L e t t , 415 (1977)
JCS Chem Corn, 427 (1977)
124
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 74A
*a *a
p y r i d ine BH
71%
AcOH
I
H
Synthesi s , 447 (1978)
Na2S204
73%
DMF/H20, r e f 1ux BZ
I
BZ
Chem L e t t , 1091 (1977) Review:
" H i g h l y S e l e c t i v e Hydrogenations over Group V I I I M e t a l s "
Strem Chemiker
Review :
E,#2,
7 (1978)
"Catal y t ic Hydrogenati on o f Aromat ic Hydrocarbons I'
Accounts Chem Res
12, 324
(1979)
Reactions i n v o l v i n g p a r t i a l r e d u c t i o n o f aromatic r i n g s ( t o o l e f i n s ) are found i n Section 200 ( O l e f i n s from Aryls).
125
DEHYDROGENATIONS TO FROM ARYLS
SECTION 748
748:
d
Dehydrogenations t o form a r y l s
KMn04
100%
benzene
A
crown e t h e r
JCS Chem Comm, 244 (1979)
0 0
a
68%
Angew I n t Ed
CuBr2, L i B r MeCN,
A
*
HO
17,278
(1978)
a
85%
T e t r L e t t , 821 (1977)
Revi ew : 'I Dehydrogena t ion o f Pol y c y c 1 ic Hydroaroma t ic Compounds " Chem Rev 78, 317 (1978)
126
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
74C:
SECTION 74D
Alkylations and a r y l a t i o n s o f o l e f i n s
No a d d i t i o n a l examples
74D:
-
Conjugate reductions
WCH0H2
+
PdCl 2/NaBH4
CHO
JOC 42, 551 (1977)
P
Li/NH3 90% ( L i bronze)
JOC 43, 4647 (1978)
Li A1 H (OMe) CuBr, THF JOC 42, 3180 (1977)
92%
SECTION 74D
CONJUGATE REDUCTIONS
127
NaH/Ni ( O A C ) ~ t-AmONa, THF JOC 44, 2203 (1979)
Chem Pharm 25, 1468 (1977)
Bull Akad USSR Chem 26, 995 (1977)
HC02
HNBu3 69%
Pd/ C
JOC 43, 3985 (1978)
128
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
THF
1 ) C8K,
e
b
SECTION 74D
A
Ph
85%
Syn thes is , 30 (1 979)
Q
NaHFe2( CO)8
p.
.8
100%
JACS 100, 1119 (1978)
* /
100%
140' C Comptes Rendus ( C )
284, 577
(1977)
H2, K3[CO(CN)5Hl 93 % NaOH, phase t r a n s f e r T e t r L e t t , 115 (1979)
SECTION 740
CONJUGATE REDUCTIONS
H2
Rh( I)-MMPP
Me
Ph
129
*
Me-h-CH2COoH / H
>92% ~70%ee
(MMPP =&-men t h y l methyl p henyl phosphi ne ) T e t r L e t t , 2487 (1977)
COOH
59%
87% HOOC
Can J Chem 56, 2269 (1978)
-
C o l l Czech Chem Comm 43, 1628 (1978) NaTeH Ph/+COOMe
EtOH
*
Ph
+COOMe 88%
Synthesis, 545 (1978)
130
COMPENDIUM OF ORGANIC SYNTHETIC METHODS
Et3N, HCOOH
VOL 4
SECTION 74E
* PhCH2CH2CN
91 %
DMF
H
Chem Pharm 25, 2396 (1977) 74E:
Conjugate a l k y l a t i o n s
100%
MerMe2NCH2CzC-]CuLi Et20
JOC
RMgX
+
CH2= CH C02Et
CuCl, Et20
44,
1006 (1979)
+ RCH2CH2COOEt
41 -80%
-40"
R = a1 k y l , Ph, benzyl
, c-Hx
JOC 42, 3209 (1977)
1 ) Me( CH2=CH)CuLi, THF
2 ) CH2=CHCH2Br
*
&-;
T e t r L e t t , 3215 (1977)
69%
4
ALKYLATIONS
CONJUGATE
SECTION 74E
(4-
(Me
131
"3 ('gBr
2
86%
Et20
Nouveau J Chem 2, 271 (1978) 0
Cu (Me)MgBr 76%
T e t r L e t t , 1591 (1977)
-$,
78%
+ zr*
a
1) N i ( I 1 )
2, H30
JACS 99, 8045 (1977)
electrolysis
S-Bu3B
+
Bu 4N I
CH3CN
S-BUCH2CH2C02Et 59%
CH2=CHC02Et BCS Japan
51, 339
(1978)
132
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
b
SECTION 74F
rt-Bu-Cu-C~c-cMe~OMe]Li
95%
JOC 43, 3418 (1978) Bu3ZnLi -2Li C1 -78O to
oo
92%
Bu
Chem Lett, 679 (1977)
P NCHzPh
1) t-BUOK
2) L-BuLi
92%
3) CH31 JACS 100, 292 (1978) 74F: Cyclopropanations
CpFe( C0)2CH2SMe2 96% 101, 6473 (1979) JACS -
SECTION 74F
P h - CH=CH2
CYCLOPROPANATIONS
CH212, Cu
*
I2 , benzene
JACS
w
H2C=CH- CC12L i
133
P
101,2139
h
d
90%
(1979)
*
39% c1
S y n t h e s i s , 425 (1979)
0-
FCH12 80%
cu
Tetrahedron 35, 1919 (1979)
C H C l 3/NaOH H20 , BzEt3NC1 77% S y n t h e s i s , 682 (1977)
134
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 75
e l ec t r o c hemi c a l reduc ti on 80% CHC13/CC14 Bu4NBr
L i e b i g s Ann Chem, 1416 (1978)
0
HCBr2C1, NaOH
*
64%
d i benzo-18-crown-6 S y n t h e s i s , 783 (1977)
CFBr3
57%
BuLi
JOC 42, 828 (1977)
S e c t i o n 75
A l k y l s and Methylenes f r o m Miscellaneous Compounds
No a d d i t i o n a l examples
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 6
PREPARATION OF AMIDES Section 76
Amides from Acetylenes
No a d d i t i o n a l examples
Section 77
Amides from Carboxylic Acids
V
aNo2 SCN, THF
A very general reaction f o r formation of amides.
JOC 44, 2945 (1979)
135
96%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
136
R-COOH
SECTION 77
-
0 tI R-C-NMe2
DMPADC
DME
%60-90%
DMPADC = N, N-dimethylphosphoramidic d i c h l o r i d e 9, 31 (1979) Synth Comm -
1 ) Catechol borane
G-H
CH3( CH2)7COOH
2,
JOC 43, 4393 (1978)
0
II
1 ) Et2N-CrC-C-Me R-COOH
85%
0 II + R-C-NR;
%go%
2) RiNH Helv Chim Acta 61, 2428 and 2437 (1 978) 1 ) Me3Si2NH
*
H2N- ( CH2)3-COOH 2) MeOH
0
0
87%
N 1 ti
S y n t h e s i s , 614 (1978)
0 I1 Ph-C-NH-CH2-C-O-N
HOOC - CH2CH2 NH2
0
0
II iI Ph-C-NH-CH2-C-NH
S y n t h e s i s , 726 (1979)
I
H00c - C Hi~ ~
AMIDES FROM ALKYLS, METHYLENES AND ARYLS
SECTION 80
137
0
QG
HOCH2COOH
+
Cl
Ph-CH-NPh
HO
*
Et3N
85% Ph
Synthesis, 407 (1977)
Related methods:
Section 78
Amides from Amines ( S e c t i o n 82)
Am,ides from Alcohols
No a d d i t i o n a l examples
Section 79
Amides from Aldehydes
Ph
P hCH=N P h
+ Me2C=C,
1 ) TiC14
81 %
2 ) LDA
O , Me OTMS
T e t r L e t t , 3643 (1977)
Section 80
Amides f r o m A l k y l s , Methylenes and A r y l s
No a d d i t i o n a l examples
138
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 81
SECTION 81
Amides from Amides
1 ) KOH, DMSO
0
II
0 I1 Ph-C-NMe2
Ph-C-NH2
99%
2 ) Me1 Tetrahedron 35, 2169 (1979)
-vc6H C6H13Br,
KOH
90%
CH= CH2
Bu4NBr
CH=CH2
T e t r L e t t , 615 (1978)
1 ) NaOH, TEBA
H‘
* ‘Bz
Z Chem
0 II Et-C-NHBz
66%
2 ) BzBr
BuBr, NaOH/H20
17,260 0
II
*
Et-C-tjBz
Bu NHS04, benzene
Bu
4eo
(1977)
I
Synthesis, 527 (1979)
82%
SECTION 81
PI t-BU-C
-
139
AMIDES FROM AMIDES
1 ) Pb(OAc)4
I
NNHTs
Q$ 0
II
98%
2) BzNH2 Angew I n t Ed 16, 728 (1977)
TeF50C4H9 *
N-C4Hg
>80%
0 JCS P e r k i n I , 2005 (1979)
0
C5H11-C-NHCH20H
8
* -t-Bu-C-NHBz
NaCNBH3 T FA
0 II C5H11 -C-NHMe
86%
Synth Comm 7, 549 (1977)
HO’
M ‘e Me
75%
Synthes s , 31 and 33 (1977)
Conjugate r e d u c t i o n s o f u n s a t u r a t e d am des a r e l i s t e d i n S e c t i o n 74 ( A l k y l s from O l e f i n s ) .
140
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 82
Amides f r o m Amines
S e c t i o n 82
0
II
Me-C-0-(salicylic
a c i d polymer)
*
Ph-NH2
Ph-NH-Ac
90%
Synth Comm 7, 57 (1977)
97% Synth Comm 7, 393 (1977)
C6F50Ac HO-CH2CH2CH2NH2
*
91 %
HO-CH2CH2CH2YH
DM F
0
p
3
JOC 44, 654 (1979)
1) PhCH2NH2
-
0
II
+
PhCNH2
2) 02 JCS Chem Comm, 970 (1979)
50%
AMIDES FROM ETHERS AND EPOXIDES
SECTION 84
Related methods:
Section 83
141
h i d e s from Carboxylic Acids (Section 77) P r o t e c t i o n o f M i n e s (Section 105A)
Amides from E s te rs
COOMe
MeZAlNHBz CH2C1
0"
ONHBz
*
T e t r L e t t , 4171 (1977)
S e ct ion 84
Amides from Ethers and Epoxides
72% HC1O4
Synthesis, 35 (1977)
78%
142
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 85
SECTION 86
Amides from Halides
I
Synthesis, 274 (1979) Boc PhCH2Br
COOMe 2) NaOH
PhCH2NH-BOC
69%
JCS Chem Corn, 758 (1977) Section 86
Amides from Hydrides
1 - adamantyl -H
By2, H2S04 MeCN
*
1 -adamantyl -NHAc
Synthesis, 632 (1977)
92%
SECTION
a7
143
AMIDES FROM KETONES
Section 87
h i d e s from Ketones
8
0 II 1) NaH, ( E ~ o ) ~ P C H ( C N ) O-~-BU
0
II
C-NHMe 94%
2 ) ZnC12, Ac20 3) QOH JACS 99, 182 (1977)
e>
H
Synthesis, 537 (1979)
0""
7) N H p ,
8~
*
2 ) VO(acac)2, A
J P r a k t Chern 319, 274 (1977)
88%
144
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 8 9
Bull Chem SOC Japan 52, 3381 (1979)
Section 88
Amides from N i t r i l e s 0 C-NH2
Na02, Me2S0 w
0"
44, 4727 (1979) JOC 1 ) KOH, t-BuOH Ph-CN
0 II
+ Ph-C-NH-C6H1
2 ) tl--CsH13-I S y n t h e s i s , 303 (1978)
Section 89
Amides from Olefins
No a d d i t i o n a l examples
85%
94%
Section 90
145
PROTECTION OF AMIDES
SECTION 90A
Amides from Miscellaneous Compounds
Fe, CH3COOH
tvleONH!-CH3
97%
Synthesis, 118 (1977)
Ph-N02
Pr-COOH
Mo(c0)6
8
63%
Ph-NH-C-Pr
JOC
2,3755
-0
A1 (Hg ) , THF/H20
'COPh
PH
100%
kHCOPh
Synth Comm
Section 90A
(1977)
2,
281 (1979)
P r o t e c t i o n o f Amides
Review: "Advances i n t h e Chemistry of t h e Acetals o f Acid Amides and Lactams" Russ Chem Rev
46,
361 (1977)
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 7
PREPARATION OF AMINES Section 91
Amines from Acetylenes
No a d d i t i o n a l examples
Section 92
Amines from Carboxylic Acids and Acid Halides
No a d d i t i o n a l examples
Section 93
Amines from Alcohols
HNMe2, 230’ ‘gH1 70H
CuO, Cr203, Na20
* C8H17NMe2
T e t r L e t t , 1937 (1977)
146
97%
SECTION 93
Ph(CH2l30H
147
AMINES FROM ALCOHOLS
HNMe2, H2
Ph(CH2)3NMe2
CuO, 240'
90%
Synth Comm 8, 27 (1978)
1
79%
Synthesis, 24 (1978)
(R)-2-octanol
1. Pyridinium salt, Et3N 2) L i N 3 , HMPA
3) LiA1H4
Pyridinium salt =
(S)-2-aminooctane
0
@OTs F
t
Y
Me Chem Lett, 635 (1977)
77%
148
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 94
SECTION 94
Mines from Aldehydes
CH=NNHPh
6
-
CH2-NHNHPh
H p 3 Pd/C
E t O H , NH3
OH
$OH OH
P
OH
S y n t h Comm 7 , 71 (1977)
El
NH
I
Mg++, THF, A
m
EtOOC
COOEt
I
H
Tetr Lett, 913 (1977)
100%
SECTION 94
AMINES FROM ALDEHYDES
HC=NPh
8
149
CH2NHPh
1) C8K, THF
*
OMe
90%
OMe
Synthesis , 30 (1 979) NaBH3( OcOcF3)
*
P hCH=NOMe
90%
PhCH2-NH2
THF Chem Pharm 26, 2897 (1978) NaBH4
P h-CH=NOH
*
OH
I Ph-CH2-N-CH2-i-Pr
65%
i-Pr-COOH
Synthesis, 856 (1977)
NaBH4
Me2C I c1
H
Y
EtOH
Rec Trav Chim 96, 242 (1977) Related methods:
Amines from Ketones (Section 102)
98%
150
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 95
SECTION 96
Amines f r o m A l k y l s , Methylenes and A r y l s
No Examples
S e c t i o n 96
Amines f r o m Amides
19
1 ) KH, THF
6
*
23)) Me1 18-crown-6
4) KOH, MeOH
84%
T e t r L e t t , 4987 (1978) 0 II Ph-C-NHPh
1) t-BuOK, e t h e r 18-crown-6
HN/Ph
\
%75%
Pr
2) P r B r
3 ) H20 Synth Corn 9, 757 (1979)
0 I1
C
Ph’
‘NH2
1) P0Cl3
PhCH2NH2
2) Zn, E t O H
Experientia 33, 101 (1977)
%go%
SECTION 96
AMINES FROM
AMIDES
151
JOC 42, 2082 (1977)
eo
1 ) Et30BF4 H N WO ‘
“M e 0
0
* 2 ) NaBH4, SnC14
M e Me0
o
m
H
80%
II S
Me-C-NHPh
-
S y n t h e s i s , 652 (1977)
Fe(C0)5
Me-CH2-NHPh
KOH
JOC 42, 3522 (1977)
JOC 42, 3522 (1977)
51 %
152
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 96
Go -(3-cH2cH 1) LiA1H4
72%
8
T e t r L e t t , 3395 (1979)
LiA1H4
MeOOC
THF
0
II
’H
C
‘NH-peptide
BH3
91%
T e t r L e t t , 1077 (1978)
38-53%
CH3-NH-peptide
TH F
JOC 42, 4148 (1977) NaBH4, BF3* Et20
I
Ar
diglyme
+
~80% 1
Ar
L i e b i g s Ann Chem, 461 (1979)
153
AMINES FROM AMIDES
SECTION 96
1) 2 EtMgBr
*
HC ( OMe )
I
NBu2
HCEt,
I
2 ) H20, NH4C1
NBu2
S y n t h e s i s , 757 (1978)
1) BuBr, NaOH
Me
Me I
I
PhCH-NH,BU
PhCH-NHCHO
91 %
2 ) H2S04 3) NaOH 4 ) HC1 gas S y n t h e s i s , 549 (1979)
; C6H51 (OCOCF,),
H2° JOC
Related methods:
44,
6
1746 (1979)
P r o t e c t i o n o f Amines ( S e c t i o n 105A)
96%
154
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 97
SECTION 97
Amines from Amines
i -PrOH, Ra-Ni
H
*
94%
(t-BuO)3Al
A Synthesis, 722 (1 977)
2C6H13-NH2
Raney-N i xyl ene , ref1 ux
* (C6H13)2NH
75%
Synthesis, 70 (1979)
steroid-NH2
1 ) CH20, MeOH
2) NaCNBH3
*
steroid-NMe2
.go%
Tetr Lett, 3469 (1977)
8
Ph-NH2
1) (Et0)2PH
*
2) BuBr, NaOH Bu NHA04
Ph-NH-BU
43
3) HC1
16, 107 (1977) Angew Int Ed -
83%
SECTION 98
AMINES FROM ESTERS
155
H2NPNH Me2CHBr
Me2CHNH
EtOH
J Prakt Chem 321, 680 (1979)
0 NI
Et
0 II 1 ) CH2=CH-O-C-C1
*
2 ) HC1
Tetr Lett,
Section 98
0 k
90%
567 (1977
Amines f r o m Esters
%60%
2 ) HCOOH
JOC 44, 3451 (1979)
156
COMPENDIUM OF ORGANIC SYNDTHETIC METHODS
Section 99
VOL 4 SECTION 100
Amines from Ethers
*
LiNH(t-Bu) -
@?
41%
NH(t-BU)
OMe
OMe
JOC 42, 2653 (1977)
S e c t i o n 100
Mines f r o m Halides
H2N-CN
NaOH, H20 2 BuBr
*
hydrolysis Bu2N-CN -Bu2NH
80%
A l i q u a t 336
Synthesis, 882 (1978)
1) + @ - - o y l : c H 2 ! - i 0
n-C8H,71
n-C H NMe2 * 817
2) LiA1H4, dioxane Angew I n t Ed 17, 274 (1978)
~50%
SECTION 100
157
AMINES FROM HALIDES
$
0
Me2N=CH2 OCOCF3 ~
~
BuLi
*
72%
BuCH2NMe2 Synth Comm
5,
539 (1976)
1) PhCH,NHOH
I
Me
PhOCH2CH2Br
*
PhOCH2CH2NH2
60%
3 ) HC1
0 P h2II P -N= CH -0E t
1 ) 3 BuMgBr w
8
Bu2CHNH3
80%
2 ) aq. NH4C1 3) HCl/THF S y n t h e s i s , 691 (1979)
0
II
n-PrBr,
E t B r , NaOH
t
P h2P-NH2 P-
NaOH
76%
II
P h2PNEt P r
phase-trans ,
Et-NH2
0
1:;
Et-NH-Pr 88% 16, 702 (1977) Angew I n t Ed -
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
158
S e c t i o n 101
SECTION 102
Amines from Hydrides
No a d d i t i o n a l examples
Section 102
Amines from Ketones
Ph
BH3.pyridine
C =,\ NNHTs
*
Et
Ph
\ ,CH-NHNHTs
95%
Et Synth Corn 9, 49 (1979)
P h - CH2NH2
1) NaBH4, AcOH
Et I
*
t
2)
82%
Ph-CH2-N-CHMe2
50'
CH3-C-CH 3
8
Synthesis, 766 (1978)
Ph-CH-C 6H
-
NNNHTS NaBH3CN \Ph
tPITHF
NHNHTs I
85%
Ph-CH-CHPh
I OH
Synthesis
, 789
(1979)
SECTION 102
d
AMINES FROM KETONES
159
O ,Me
NaBH3( OCOCF,)
90%
TH F Chem Pharm
-
26, 2897
(1978)
HO-N-CH2CH2CH3
NaBH4
87%
CH3CH2COOH
Synthesis, 856 (1977)
1 ) LiA1H4
83%
T e t r L e t t , 2737 (1977)
Me
/ +M!*e
A Me Ph
1) LiA1H4
H-
* IC - NH2 I
I
2 ) H',
MeOH
Ph 78%ee
JCS Chem Corn, 723 (1977)
~50%
160
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 103
Related methods: Amines from Aldehydes (Section 94)
S e c t i o n 103
Amines from N i t r i l e s
9
BH30H
Ph-CN
89%
Ph-CH2NH2 JOC 42, 3963 (1977)
H2 Y [RhH(L-Pr3P)31
*
Me ( CH2)4CN
Me( CH2)4CH2NH2
100%
TH F JCS Chem Comm, 870 (1979)
1 ) MeMgI CN
2)
e M g B r
Me
3) H20 T e t r L e t t , 23 (1977)
NC
I
R- C-H
I
H
1 ) BuLi
2 ) BzBr
R- C-BZ
I
H
L i e b i g s Ann Chem, 40 (1977)
61%
SECTION 105
Section 104
AMINES FROM MISCELLANEOUS COMPOUNDS
161
Amines from O l e f i n s 1 ) PdCl ( PhCN)2 2 ) Me2NH
*
C8H1 7-CH=CH2
81 %
C 8H 17-CH-NMe2 I
3) MCPBA 4) KBH4
CH2NMe2
T e t r L e t t , 163 (1978)
A -
Me
i
MeNHCl
Ph
51 %
Me-#\ Ph
J P r a k t Chem 320, 413 (1978) 1 ) MeNH2, PdC12(PhCN)2
*
C8H1 7-CH=CH2
43%
2) Br2 ‘gH1 7 JCS Chem Comm, 413 (1977) S e c t i o n 105
Amines from Miscellaneous Compounds
92%
OMe
OMe JACS 99, 98 (1977)
162
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 105
H20, CO, Fe(CO)5 Ph-N02
w
Ph-NH2
JACS
100,3969
100%
glyrne, E t 3 N (1978)
Cl
c1
Angew I n t Ed 16, 41 (1977) NH,
Fe(II1) oxide 92% N2H4, YeOH
Me
Me Synthesis, 834 (1978)
bC1bcl N2H4, Pd-C
100%
CH3
THF/ ethanol
*
CH3
Synthesis, 850 (1977)
SECTION 105
AMINES FROM MISCELLANEOUS COMPOUNDS
-
163
Et3N*HCOOH
Ph-NOZ
Ph-NH2
100%
Pt/C
JOC 42, 3491 (1977)
H2
hC
100%
Ru c a t a l y s t
IEC
I CMe2 I OH
I
4
JOC
H2, Ra-Ni CH20 MeOH,
44,
1233 (1979)
60%
COOMe
Q
CH2CH2N3
N02
I n d i a n J Chem 148, 904 (1976)
c:: Et3N, MeOH
Q
CH2CH2NH2
N02
T e t r L e t t , 3633 (1978)
95%
164
CONPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 105
CrCl
Ph-N02
97%
Ph-NH2
CH30H
S y n t h e s i s , 792 (1977)
Y
CrCH
C-CH
cosx
90%
NH2 JOC
L
5, 3671
(1979)
paraffin 78% 4COo
C@CH3
COCH3 S y n t h e s i s , 23 (1 978)
6
N 13 TMSO-CH
CH NH
l 2
93%
T e t r L e t t , 2737 (1977) Review: "0-Mesi t y l e n e s u l f o n y l hydroxylamine and R e l a t e d Compounds-Powerful G i n a t i n g Reagents" S y n t h e s i s , 1 (1977)
SECTION 105A
PROTECTION OF AMINES
165
Review: "General Methods o f A1 k a l o i d S y n t h e s i s " Accounts Chem Res
S e c t i o n 105A
2,193
P r o t e c t i o n of M i n e s
R e l a t e d methods: h i d e s f r o m Amines ( S e c t i o n 82); h i d e s ( S e c t i o n 96)
CH 1 2 CHMe2
(1977)
HCOOH
~ ~ ~ - c H -coo-t-~~
Amines f r o m
R I
CH2 CHMe2
H-C-NH-CH-COO-t-Bu -
DCC
87%
JOC 42, 2019 (1977) R I
H2N-CH-COOR'
0 1 I1 [H-C-0-C-H]
in situ +
OT\NMe/CH2Cl
w
if:
H-C-N-CH-COOR' 1 H
S y n t h e s i s , 709 (1979)
1w c H 2 i + N o 2 2 ) PhCOCl H2N( CH2)aNH2
*
1
81 %
H2N( CH2)8NHCPh
3 ) TFA I s r a e l J Chem
lJ,
248 (1979)
166
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
R
I
H2N-CH-COOH
0
It
EtO-C-CF3
O R II 1 F3C-C-NH-CH-COOH
SECTION 105A
~80-90%
E t 3 N , MeOH
JOC 44, 2805 (1979)
Use of t h e p-hydroxybenzyloxycarbonyl p r o t e c t i n g group i n p e p t i d e s y n t h e s i s . Removed by H202/NH3. Tetrahedron 34 31 05 (1 978)
0 R-NH-C-O-C(Me2)CC1 II
R-NH2 Zn/HOAc
Angew I n t Ed 17, 361 (1978)
8 / Use o f t-BuO-C-N=C,
\
Ph as a t-butyloxycarbonylating reagent.
COOE t BCS Japan 50, 718 (1977)
Z-peptide
-
H2N-peptide
Pd/C
JCS P e r k i n I
490 (1977)
PROTECTION OF AMINES
SECTION 105A
BOC- Gly-OBZl
1) Me3SiSiMe3/12
*
167
glycine
100%
2 ) H20
Angew Int Ed 18, 612 (1979) TsOH
Boc-Trp-OH
*
dioxane/anisole
H2N-Trp-OH
Chem Pharm Bull
100%
26, 2198
(1978)
Boc and Z(0Me) protecting groups are removed by ethanesulfonic acid i n acetic acid or methylene chloride. Z, benzyl ester, G methoxybenzenesul fonyl groups are , and n-P_ S-p-methoxybenzyl unaffected. Chem Pharm Bull 25, 740 (1977)
1 , 4-cyclohexadiene/Pd-C removes N-benzyloxycarbonyl protecting groups. JOC 43, 4194 (1978)
168
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 1 0 5 A
&p-N02 0
II
CH20C-NHR
R-NH2
8 8 or CF3COOH JOC
R-y
-O ! CH2{ H
42,
399 (1977)
*
R-NH2
CH2C1
JCS Chem Comm, 450 (1978)
SECTION 105A
169
PROTECTION OF AMINES
8
NH - C - 0 C H
R-NH2
2
0
H2/cat.
JOC 42, 3286 (1977)
JCS Chem Comm, 358 (1978)
Peoc group:
0 II R3PCH2CH2-O-C-
Q
Enhances t h e w a t e r - s o l u b i l i t y o f p r o t e c t e d amino a c i d s and peptides; extremely r e s i s t a n t t o a c i d s , i n c l u d i n g TFA. Removed by weak bases. 17, 67 (1978) Angew I n t Ed Use o f t h e l-methylcyclobutyloxycarbonyl p r o t e c t i n g group i n p e p t i d e synthesis. More s t a b l e than t-Boc toward HOAc.
H
JOC
42,
143 (1977)
170
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 105A
Adpoc = -C-0-C(Me2)-1 -adamantyl
Ad POC- N H - R
R-NH?
Stab1 e toward h y d r o g e n o l y s i s
.
Angew I n t Ed 17, 944 (1978) I
Me-cYo-y-
t-Boc group. i s more s t a b l e t o TFA t h a n i s t h e 0 Me
I
Rl
C1 eaved by HBr/HOAc
JCS P e r k i n I, 1459 (1979)
0 R-NH-IE-0-
o r 1 ) B r p , 2 ) MeOH
T e t r L e t t , 1563 (1977)
SECTION 105A
PROTECTION OF AMINES
KF, 1 8 - c r o w n - 6
or HF o r H2NNH2 JCS P e r k i n I , 627 ( 1 9 7 7 )
R-NH2
JCS Chem Comm, 220 (1978)
171
172
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4 SECTION 105A
hv
R2NS02Bz
R2NH
-i-PrOH
T e t r L e t t , 1029 (1978)
10% Pd/C cyclohexene or NaH2P02
*
R2NH
0 T e t r L e t t , 555 (1979)
R-NH2
Chem Pharm B u l l 26, 296 (1978)
SECTION 105A
peptide-NH2
PROTECTION OF AMINES
IHC1-dioxane
173
/
Chern L e t t , 7 (1978)
100% 02N'
HOAc
R = peptide AZOC, BPOC, BOC, t - b u t y l e s t e r , MSOC, and Tos are u n a f f e c t e d by the reaction conditions, Helv Chim Acta 61, 1086 (1978)
4
1 ) EtOCSCH2COOH 2 ) ClSCOCl R-NH2
*
Et3N JACS
99, 7363
(1977)
174
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
R2NH
5
I0I
SECTION 105A
,, 5
R2NCCH2NHCSBz T FA
T e t r L e t t , 325 (1979)
1)
Me0
0
,
Me4NOH
R-NH2
26, 660 (1978) Chem P h a r m B u l l -
SECTION 105A
PROTECTION OF AMINES
Ph ph$o 0
Yellow, fluorescent derivatives.
42, 2819 (1977) JOC Review : "Protecting Groups in Peptide Synthesi s " Chem & Ind, 617 (1979)
175
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 8
PREPARATION OF ESTERS Section 106
Esters from Acetylenes
No a d d i t i o n a l examples
Section 107
Esters from Carboxylic Acids and Acid
Halides
The f o l l o w i n g types o f r e a c t i o n s are found i n t h i s s e c t i o n : 1. Est ers from c a r b o x y l i c a c i d s (and a c i d h a l i d e s ) and a l c o h o l s .
2. Lactones from hydroxy acids.
3 . Esters from c a r b o x y l i c acids and h a l i d e s , s u l f o n a t e s , and m i s c e l l aneous compounds. 0
It C-OEt
CH3CH21
anion-exchange r e s i n JOC 44, 2425 (1979)
176
94%
ESTERS FROM CARBOXYLIC A C I D S AND A C I D HALIDES
SECTION 107
177
CH3GN=?HMe NH
*
F&CH20COMe
{
-N
’
CH20COMe 72%
COOH
T e t r L e t t , 5219 (1978)
-
Me3C-COOH
DBU
t
benzene
0 II Me3C-C-0Bu
Bu-Br
81 %
BCS Japan 51 , 2401 (1978)
COOH
Ph
Q
MeOH, DCC
*
Ph-
COOMe
98%
Angew I n t Ed 17, 522 (1978)
CH2COOH EtOH, DCC
96%
Br
T e t r L e t t , 4475 (1978)
178
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Ph-CH2CH2COOH
-
SECTION 107
8
DCC, TsOH
Ph-CH2CH2C-O-i--Pr
c
99%
p y r id i ne
i-PrOH
Acts Chem Scand B, 33, 410 (1979)
DCC
*
lauric acid t
cholesteryl laurate 67%
cholesterol Synth Comm 9 , 539 (1979)
M
e
O
e
COOH
H
G
8
PC-0
PPE, DMF
85%
Synthesis, 429 (1979)
P ( OMe
Ph-COOH
8
Ph-C-OMe
JOC 43, 4672 (1978)
9 0%
SECTION 107
ESTERS
FROM
CARBOXYLIC ACIDS AND A C I D HALIDES
179
8 PhOPOCl 81 %
Ph ( CH2 I30H , p y r i d i ne
T e t r L e t t , 4461 (1978)
( Ph2CH0)3P=0 Q HC O O H
*
TFA, CH2C12
83%
(&I C-OCHPh2 H
T e t r L e t t , 4697 (1978)
EtOH, p y r i d i n e Z-G1 y-Tyr-OH
*
Z - G 1y -Tyr - 0Et
95%
(PhO) PBu 31 Br Synthesis, 355 (1979)
0
Me30BF4 R-COOH
R = a1 k y l , a r y l
II
+
R-C-OMe
, vinyl JOC 44, 1149 (1979)
..go%
180
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL
4
SECTION 107
Me3SOH
R-COOH
R-COOMe
100%
JOC 44, 638 (1979)
8
1. Ph3P,
*
R-C-OH
a
R-C-OE t
%70-80%
2. E t O H R = cephalosporinic acid,
Chem L e t t , 979 (1978)
f (
‘
y OH
c=o Ph
BF4
BzEt 3 N C1
Ph Chem L e t t , 441 and 763 (1977) Chem L e t t , 885 (1978)
SECTION 107
ESTERS FROM CARBOXYLIC ACIDS AND A C I D HALIDES 181
2 ) EtOH, Bu3N
BCS Japan 50, 1863 (1977)
1)
*
Me2CHCOOH
0 II Me2CH-C-O-t-Bu -
91 %
2) t-BUOH
-
Chem L e t t , 145 (1979)
@O
H3N-CH-COB
TsOH, EtOH
R
80 TsONH3-&H-COOEt
r e f 1ux
B u l l Chem SOC Japan 52, 1879 (1979)
1 ) cs2c03
Boc-Pro-Pro-OH
Boc-Pro-Pro-OBz
2 ) BzBr
JOC 42, 1286 (1977)
96%
182
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4 0 II Br-CH2-C-Ph
*
Me3C- COOH
SECTION 108
0 8 II Me3C-C-OCH2CPh
95%
KF, DMF T e t r L e t t , 599 (1977) BOP, E t 3 N w
Boc-Trp-OH
96%
Boc-Trp-OPh
CH2C12, PhOH
Synthesis, 413 (1977) Further examples of t h e r e a c t i o n RCOOH t ROH
-+
RCOOR are included
i n Section 108 (Esters from Alcohols and Phenols) and Section 10A ( P r o t e c t i o n o f Carboxylic Acids).
Section 108
Esters from Alcohols and Phenols
OH
Ph
-CI -CH3 I
Ph
OAc
I
Et3N, Ac20
Ph -C-CH3
&
I
Ph
0 Tetrahedron
34,
2069 (1978)
92%
ESTERS FROM ALCOHOLS AND PHENOLS
SECTION 108
183
Synth Comm 7, 383 (1977)
JOC (USSR) 13, 608 (1977)
e
PhCOCl
*
H3N(CH2)40H MeCN/benzene
c10
0 II H3N(CH2)40-C-Ph
@
58%
ClQ
Synth Comm 8, 327 (1978) 0
II
Ph-C-0-(sal i c y l i c a c i d polymer) BuOH
a
* Ph-C-OBU Synth Comm 7, 57 (1977)
77%
184
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4 0 ll
PPh3, benzene
OH
( MeOOC)$=o, PhCOOH
SECTION 108
b&
( i nversion )
72%
T e t r L e t t , 3179 (1977)
6
8
0 II O-C-H
fiH2
HC-O-C-CH20Me
>go%
Et3N Rec Trav Chim
98, 324
(1979)
e;' 8
4 OH
ci M e 2 N a N
, benzene
b
>95%
Bull Chem SOC Japan 52, 1989 (1979)
ESTERS FROM ALCOHOLS AND PHENOLS
SECTION 108
185
t- [P t C1 ( C7H4)AcIm] Me
100%
CH2CH2CH20H
CH2CH2CH20Ac AcIm = N - a c e t y l i m i d a z o l e JACS
99, 3531
(1977)
0
II
Ph-C-CN a c y l a t e s s t e r o i d a l c o h o l s s e l e c t i v e l y i n t h e o r d e r 21 > 17 8> 38> 6a, 3a>> 20a>208> 7 8>> 7a> 68>22 8>22a C o l l Czech Chem Commun 44, 2443 (1979) Review: " 4 - D i a l k y l ami n o p y r i d i n e s as H i g h l y A c t i v e Acyl a t i o n C a t a l y s t s II Angew I n t Ed 17, 569 (1978) K I , electrolysis C5H1 CH20H
*
0 II C5H11 C-O-L-Bu
83%
H20, t-BuOH T e t r L e t t , 165 (1979)
F u r t h e r examples o f t h e r e a c t i o n ROH -+ R ' C O O R a r e i n c l u d e d i n S e c t i o n 107 ( E s t e r s f r o m C a r b o x y l i c Acids and A c i d H a l i d e s ) and S e c t i o n 45A ( P r o t e c t i o n o f A l c o h o l s and Phenols).
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
186
Section 109
Esters from Aldehydes
OCH0
SECTION 109
n
C-OMe
03, MeLi
Me OH/ TH F
63%
Tetr Lett, 1627 (1978)
CH3( CH2)8CH0
8
NBS, hv
CH3(CH2)8C-OEt
t
E tO-TMS JOC 43, 371 (1978)
i
0 SCH
Me0
1 3 1 ) CH2SCH3, base 2) EtOH, HC1
CH2C-OEt
*
~85% OMe
Bull Chem SOC Japan
52,
2013 (1979)
187
ESTERS FROM ALDEHYDES
SECTION 109
Me2C=C( OMe ) 1 ) ZnC12-
t
2 ) H30@
Ph-CH-CMe2
t
I HO
I COOMe
80%
Ph-CHO Synthesis, 400 (1978)
0
Cr03, pyrOHC1 90%
T e t r L e t t , 3483 (1977)
anodic o x i d a t i o n 0‘
*
MeOH, KOH
n
0\c/o
Pr’
72%
O ‘ Me
Synthesis , 283 (1978)
0 It CH3-C-Br
-i-Bu-CHO
ZnCl
i-Bu-CH-OAc I Br
Synthesis, 593 (1978)
99%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
188
6
1 ) Et3SiOP(NMe2)2
0
2) BuLi 3)
JCHo Ph
SECTION 111
p
h
6
65%
JACS 101 , 371 (1979)
Related methods:
Section 110
E s te rs from Ketones (Section 117)
Esters from Alk.vls, Methylenes and A r y l s
No examples o f t h e r e a c t i o n RR
-f
RCOOR' o r R'COOR (R,R'=al k y l ,
a r y l , e t c . ) occur i n t h e l i t e r a t u r e .
For t h e r e a c t i o n RH
o r R'COOR see Section 116 (Esters from Hydrides).
Section 111
-+
RCOOR'
E s te rs from Amides S
1 ) Me1 , MeOH
M
e
90 -OMe
3
*
Me3cv-NMe2
100%
2 ) aq.K2C03
Me
Me JACS
101,1316
(1979)
ESTERS FROM ESTERS
SECTION 113
Section 112
189
Esters from m i n e s
Ph-CH2CH2NH2
+
-i-AmONO
14
CH3-C-OCH2CH2Ph
CH3COOH
Synth Corn
&,
84%
33 (1978)
Ph
8
Bu-O-C-Ph
BuCH2NH2
85%
2) PhCOONa
JCS Chem Corn, 701 (1977)
Section 113
Esters from Esters
Conjugate redudtions and conjugate a l k y l a t i o n s o f unsaturated
-
e s t e r s are found i n Section 74 ( A l k y l s from O l e f i n s ) .
Ph-CH2 -COOEt
1 ) CgK
2) Me1
P h -CH-COOEt 1
Me
T e t r L e t t , 653 (1977)
70%
190
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
6
1 ) PhSCH2CZ,
ZnBr2 o r TiC14
H'
+
2 ) NaI04
3)
SECTION 113
90%
T e t r L e t t , 993 and 995 (1979)
+,PhI
L iCH2 C -0
PhCH2C-0
N i B r 2 , BuLi
JACS
99, 4833
+,
73%
(1977)
boric acid
- F 180"
C02Me 92%
Synth Corn 9, 609 (1979)
ESTERS FROM HALIDES AND SULFONATES
SECTION 115
191
18, 793 (1979) Angew Chem I n t Ed Section 114
Esters from Ethers
Ph- I(OCOCF 3 )
*
R-OBZ
0 II R-O-C-CF3
42-100%
R = n - a l k y l , Ph, Bz
JCS Chem Corn, 615 (1979) BzEt3NMn04 ' Q
-n-Bu-O-CH2Ph
*
8
BU-O-C-Ph
90%
CH2C1 Angew I n t Ed 18, 68 and 69 (1979) Section 115
Esters from Halides and Sulfonates
I - (CH2) 15-COOH
cs2c03
DMF
JCS Chem Comm, 286 (1979)
85%
192
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
1) W 0 ) 5
*
Bu-MgBr
SECTION 116
0
I
Bu-d-OBz
73%
2 ) BzOH, I 2
T e t r L e t t , 1477 (1978)
Br
T e t r L e t t , 1455 (1978)
R e l a t e d methods: C a r b o x y l i c Acids f r o m Hal i d e s ( S e c t i o n 25)
S e c t i o n 116
E s t e r s f r o m Hydrides
T h i s s e c t i o n c o n t a i n s examples o f t h e r e a c t i o n RH
+
RCOOR' o r
R'COOR ( R = a l k y l , a r y l , e t c . ) .
Ag 0 59% TFA, TFAA Synth Comm
5,
543 (1976)
ESTERS FROM HYDRIDES
SECTION 116
193
4 Q 0
II
oNC\ph
PhCOOH, TSP TFA
OCH3
97%
OCH3
(TSP = 2 - t r i fluoromethanesul f o n y l o x y p y r i d i ne)
Chem L e t t , 1099 (1977)
Se02, L i B r
004c OAc T e t r L e t t , 3279 (1978)
Also v i a :
C a r b o x y l i c a c i d s , S e c t i o n 26; A l c o h o l s , S e c t i o n 41
194
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 117
SECTION 117
Esters from Ketones 0 II TMS-0-S-0-0-TMS
96%
I1
0
JOC 44, 4969 (1979)
83% \ JCS Chem Corn, 870 (1977)
BF3* E t 2 0
0
AcOOH
0
Acta Chem Scand ( B ) 32, 467 (1978)
SECTION 118
6
195
ESTERS FROM NITRILES
8C-OMe
0
II
1 ) NaH, (EtO)2PCH(CN)O-t-Bu
85%
2) ZnC12, Ac20
3) %Me
JACS
99, 182
bH
(1977)
i Me3
Me3Si
*
*
JCS Chem Comm, 772 (1977) Also via Carboxylic acids, Section 27 Section 118
Esters from Nitriles
No additional examples
73%
196
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 119
SECTION 119
Esters from Olefins
1 ) LiA1H4, TiC14
*
/ -
-0Ac
58%
2) P ~ ( O A C ) ~
*c
T e t r L e t t , 1405 (1979)
0
g
03, HC1
COOMe
COOMe
CH30H
85%
Angew I n t Ed 17, 939 (1978)
1 ) Pb(OCOPh)4
OCOP h
66% 2) Et4NF
OCOPh
JOC 42, 1051 (1977)
80% JACS 101, 3884 (1979) A l s o v i a A l c o h o l s , S e c t i o n 44
OF ESTERS
SECTION 120A
PROTECTION
Section 120
F s t e r s from Miscellaneous Compounds
BzBr
+
-
08
iL2O N,? OLi
MeOOC
&
T e t r L e t t , 1161 (1977)
Section 120A
P r o t e c t i o n o f Esters
HgO, BF3* THF
*
197
8
R-C-OR'
Synthesis , 223 (1 979)
NO2
80%
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 9
PREPARATION OF ESTERS AND EPOXIDES S e c t i o n 121
E t h e r s and Euoxides from Acetylenes
No examples S e c t i o n 122
E t h e r s and Epoxides from C a r b o x y l i c Acids
No a d d i t i o n a l examples S e c t i o n 123
R-OH
E t h e r s and Epoxides f r o m A l c o h o l s and Phenols
CH2N2
R-OCH3
s i l i c a gel
T e t r L e t t , 4405 (1979)
7 98
25-98%
SECTION 123
ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS
199
1 ) KOH, DMSO Ph2CHOH
Ph2CHOMe
b
97 %
2 ) Me1 Tetrahedron 35, 2169 (1979) CH3C1, benzene
*
H- ( OCH2CH2)4-OH
H3C-(OCH2CH2)4-OCH3
NaOH, H20
95%
Synthesis, 123 (1979)
n-C6H1 3-OH
+
N i (acac)2
81 %
n-C6H13-0-Bz
Bz-Cl Synthesis, 803 (1977)
- -f Et2S04
-OH
W
KOH/ DMSO
O
E
t
70%
Synthesis, 428 (1979)
(33
Et30BF4
CH20H
CH20Et
JOC 42, 1801 (1977)
89 %
200
COMPENDIUk OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 123
0
I1
P ( OCHPh2)3
Bu-OH
*
74%
Bu-OCHPh2
TFA, CH2C12
a\,
T e t r L e t t , 3943 (1978)
Me2N R-OH
Ph3CC1 b
R-0-CPh3
Et3N, DMF
T e t r L e t t , 95 and 99 (1979)
90%
JOC 43, 4672 (1978) I
00
Me3SOH 100%
Ar-OMe
Ar-OH
-
JOC
44,
638 (1979)
80
Me3SeOH
Ph-OH
Ph-OMe T e t r L e t t , 1787 (1979)
100%
SECTION 123
ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS 201
Bu-I
Ph-OH
83%
Ph-0-Bu
KF/Cel i t e
Chem L e t t , 45 (1979)
pyridine
PhOH + t-BuBr
90%
Ph-0-t-Bu -
30"
Chem L e t t , 57 (1978) Ph-OH
Et4NF
t
EtI
75%
P h-0-E t DM F
Can J Chem
57,
1887 (1979)
Related methods: P r o t e c t i o n o f Alcohols (Section 45A). NCOOEt
II
NCOOEt
95%
NCOOEt NCOOEt
0
Ph3P T e t r L e t t , 5153 (1978)
100%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
202
H
SECTION 123
H
DMSO
99% 175"
JOC 42, 2012 (1977)
1. EtMgBr
( CH3)3C-OH
2*
Q
w'
Chem L e t t 817 (1977)
\ HU'
H2, MeOH P t ( 11)-Sn(I1)
complex c a t a l y s t
%loo%
OMe
Chem L e t t , 835 (1978)
ETHERS AND EPOXIDES FROM ALDEHYDES
SECTION 124
203
Synthesis, 706 (1977) Related methods:
Section 124
MeO,
Ethers and Epoxides from Aldehydes
Me3SiH
O ,Me C
! PI
P r o t e c t i o n of Alcohols and Phenols ( S e c t i o n 45A)
H‘
+ -
Pr-CH20Me
100%
Me3Si OTf T e t r L e t t , 4679 (1979)
NaCNBH3
CH3( CH2)8CH20Me
HC1 ( 9 ) , MeOH
83%
T e t r L e t t , 1357 (1978) 2LiA1 H4-TiC14 PhCH2CH2CH20Me 87%
BCS Japan 51, 2059 (1978)
204
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
py-BH3/CF3COOH PhCHO
*
PhCH2-O-CH2Ph
-Q
SECTION 124
87%
CH20(CH2)6CH3
py -BH3/ CF3COOH c1
CH3( CH2)60H
c1
82%
Chem Pharm B u l l 27, 2405 (1979)
*
2PhCHO
PhCH20CH2Ph
87%
2 ) H30Q Chem L e t t , 415 (1979)
(@-?Me2 Ph-CHO
*
Ph
97%
T e t r L e t t , 203 (1979) Re1 a t e d methods : E t h e r s and Epoxides f r o m Ketones ( S e c t i o n 132)
SECTION 128
S e c t i o n 125
ETHERS AND EPOXIDES FROM ESTERS
205
E t h e r s and Epoxides f r o m A l k y l s , Methylenes and A r y l s
No examples o f t h e p r e p a r a t i o n o f e t h e r s and epoxides b y r e p l a c e ment o f a1 k y l methylene and a r y l groups o c c u r i n t h e l i t e r a t u r e . F o r t h e c o n v e r s i o n of RH -+ ROR' ( R , R ' = a l k y l ) see S e c t i o n 131 (Ethers from Hydrides)
S e c t i o n 126
E t h e r s and Epoxides, f r o m Amides
No a d d i t i o n a l examples
S e c t i o n 127
E t h e r s and Epoxides f r o m Amines
No a d d i t i o n a l examples
S e c t i o n 128
E t h e r s and Epoxides f r o m E s t e r s
0-77%
Chem and I n d
230 (1977)
206
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 129
SECTION 130
Ethers and Epoxides from Ethers and Epoxides
'"Yote
A1 C1
76%
JCS Chem Comm, 382 (1979) Section 130
Ethers from Halides and Sulfonates
0
Resin (Ph-0 )
benzene
t
*
Bu-0-Ph
100%
Bu-Br Synthesis, 113 (1977) Ph-OH
Et4NF
t
EtI
*
Ph-0-Et
75%
DMF
Can J Chem
57,
1887 (1979)
ETHERS FROM HYDRIDES
SECTION 131
*
PhCH2Br
207
PhCH20CH2CH2Br
90%
Et4NI T e t r L e t t , 2639 (1979)
0
0
PhONa
80% 6
Synthesis
0
PhO
, 298
0
P
h
(1977)
, DMF
_____)
F
PhO
0
JOC 42, 3425 (1977)
Related methods: Ethers from Alcohols (Section 123)
Section 131
Ethers from H-ydrides
No a d d i t i o n a l examples
0
85-95%
208
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 132
E t h e r s and Epoxides f r o m Ketones
a
Me-S-CH2Na I1
NTs ( 3 eq.)
es t r o n e
SECTION 132
8
96%
DMSO
JACS 101 , 6135 (1979)
Me3Si H
76%
Me3Si OTf
T e t r L e t t , 4679 (1979)
NaCNBH3 78% HCl(g), MeOH
T e t r L e t t , 1357 (1978)
II 0
P h- C-CH3
*
Ph-!
4 Me
T e t r L e t t , 203 (1979)
94%
SECTION 134
ETHERS AND EPOXIDES FROM OLEFINS
0
1 ) NaBH4
Ph-C-C(Me2)SMe II
__T
2 ) Me1
Ph
209
AMe Me
68%
JCS Chem Comm, 785 (1978)
Related methods:
S e c t i o n 133
Ethers and Epoxides from Aldehydes ( S e c t i o n 124)
Ethers and Epoxides from N i t r i l e s
No a d d i t i o n a l examples
S e c t i o n 134
Ethers and Epoxides from O l e f i n s
H2°2
H./f
P,
JCS Chem Comm, 948 (1977)
210
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 134
0 011
EtOCCl
85%
JOC 44, 2569 (1979)
CH3C( O E t ) b
H2°2
(yo
99%
T e t r L e t t , 1001 (1979)
0 II PhSeOH, H202 75% buffer
+
JOC 42, 2034 (1977)
"z02
Ph
ArSeOOH
Ph
Synthesis, 299 (1978)
91%
SECTION 134
21 1
ETHERS AND EPOXIDES FROM OLEFINS
H202, HOAc, EtOAc
28%
T e t r L e t t , 1369 (1977)
\
*6
T e t r L e t t , 623 (1977)
6
t-BuOOH, t r i f l uoroacetyl camphor
78%
PhCH3, Mo02(acac)2
82%ee
Z Chem 18, 218 (1978)
212
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 134
OOH
CF~-~-CF~ AH
90%
JACS 101, 2484 (1979)
MCPBA, CH2C1 95% pH 8 phosphate b u f f e r
d
JOC 44, 1351 (1979)
MCPBA , NaHC03
H20, Ct12C12
59%
T e t r L e t t , 427 (1977)
t-BUOH
75%
B u l l Akad USSR Chem 27, 387 (1978)
ETHERS AND EPOXIDES FROM OLEFINS
SECTION 134
21 3
N-benzoyl peroxy-carbami c a c i d 0
89%
THF
&
JOC 44, 1485 (1979)
p h a sNaoC1 e-transfer *
&go%
JACS 99, 8121 (1977)
1 ) 12, MeCN
OP03Et2
64%
2 ) NaOEt, THF
JACS 99, 4829 (1977)
CH3CH0, O2 hu, PhCl
*
S y n t h e s i s , 711 (1977)
214
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 135
1 ) N-iodosuccinimide 2) KOH T e t r L e t t , 2545 (1979)
8
PhSeCl
8
I
SePh
83%
89%
T e t r L e t t , 1257 (1977)
-
JACS 102, 3784 (1978) Section 135
Ethers and Epoxides from Miscellaneous Compounds
Ph-S-CH2CH2Ph II
N-TS
1 ) NaH, THF
2 ) PhCHO
H--{ l l - C H 2
Ph
H
Synthesis, 693 (1977)
Ph
80%
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 10
PREPARATION OF HALIDES AND SULFONATES Section 136
Halides from Acetylenes CuCl 2-Li C1
Ph-C-C-Et
Ph \ c=,c
*
MeCN
/cl
c1
94% Et
100%
JCS Perkin I , 676 (1977)
0 C r CH
1) LiA1H4 2 ) Acetone ~
9
/c=c\cl/ I
H
3) IC1
JAG 101, 5101 (1979)
21 5
89%
216
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 136
0 0
Et3NH HC12 Ph-CECH
*
Ph
73%
\
\
/C=CH2
JCS P e r k i n I,1797 (1977)
Ph
1 ) TeC14
Ph - C X - Me
\
+
/c=c\I
2 ) 12, MeCN
/
Me 85%
c1 Chem L e t t , 1357 (1979)
1 ) Cp2ZrC12, Me3A1
Bu-CZC-H
*
2 ) 12, THF
Bu
\
/H
/c=c\, Me
85%
S y n t h e s i s , 501 (1 979)
1 ) [EtCuBrlMgBr
Ph
2 ) NBS
Q Et-CEC-Et
TH F
\
/H /C=C\Br Et
w
Ph-CGCH
>go%
96, 168 (1977) Rec Trav Chim -
(HF)n
* 7 75%
F
F
HALIDES AND SULFONATES FROM ALCOHOLS
SECTION 138 Section 137
21 7
Halides from Carboxylic Acids
HgO, Br2
0
2
b
B
r
97%
CC14, hv
02N
(0% y i e l d w i t h o u t l i g h t )
JOC
9, 3405
(1979)
Hal i d e s and Sulfonates from Alcohols
Section 138
- 6
Me3Si Br
90%
T e t r L e t t , 4483 (1978)
H\ /OH
Me3Si I ._____)
CH3 "\C6H,
I
A\ CH3
95%
'sHl
3
>90% i n v e r s i o n T e t r L e t t , 2659 (1977) OH I
Me3SiC1, NaI MeCN
-6
Synthesis, 379 (1979)
85%
218
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 138
Me3Si C1
98 %
Na I
JOC
44,
OH
4
1247 (1979)
-4 i
1 ) Me3SiSiMe3/12 2) H20
86%
Angew I n t Ed 18, 612 (1979) 1 ) Me3SiCI, p y r i d i n e Ph-CH-CH2COOEt AH
*
2 ) PhPF4
Ph-CH-CH2COOEt
;
92%
T e t r L e t t , 4507 (1978)
PPh3
CH2'CH-CH-CH3 I
OH
CH2=CH-CH-CH3
c1 3cccc1
!
I
c1
T e t r L e t t , 2999 (1977)
94%
SECTION 138
HALIDES AND SULFONATES FROM ALCOHOLS
-
21 9
DMPADC*
PhCH20CH2CH20H
,!*
PhCH20CH2CH2C1
92 X
l-Dimethylphosphoramidic d i c h l o r i d e Chem L e t t , 923 (1978) HC1, ZnC12 R-OH
+
R-C1
tri nonyl b o r a t e
R = 1" a l k y l
JOC (USSR)
13,604
(1977)
>90% i n v e r s i o n
Chem L e t t , 383 (1977)
%80% HO
F T e t r L e t t , 1823 (1979)
220
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
s
SECTION 138
T e t r L e t t , 4575 (1978)
c1 3c-c-cc1
+
100%
Ph3P
CH2C1
JOC 44, 359 (1979)
T f OTf
R-OH
R-OTf
213-89%
pyr id in e
JOC 42, 3109 (1977) PhS02C1 , benzene Bu-CH20H
Bu-CH20S02Ph
S y n t h e s i s , 822 (1979)
85%
SECTION 139
HALIDES FROM ALDEHYDES
221
-
Aust J Chem 30, 2479 and 2487 (1977)
Section 139
Hal i d e s from A1 dehydes
72%
Synth Corn
9,
341 (1979)
90% ’H
DMF JOC
43,
4367 (1978)
222
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 140
Halides from Alkyls
b
O N
HC1
CH3CN
ASection 141
+
h
Synthesis, 227 (1978) HBr Helv Chim Acta
$-
Br 94%
62,
2338 (1979)
RHal see Section 146 (Halides from Hydrides)
Halides and Sulfonates from Amides
No additional examples
76%
CH2C7
HOAc
For the conversion RH
SECTION 141
SECTION 142
HALIDES FROM AMINES
223
H a l i d e s from Amines
S e c t i o n 142
Ph
Bu-NH2
4;;
4
69%
S y n t h e s i s , 634 (1977)
*
t-BUSNO MeCN, CuC12
N02
98%
N02
T e t r L e t t , 4519 (1978)
t-BUONO,
CUCl
MeCN
N02 JOC
42,
6 N02
2426 (1977)
12, benzene Chem L e t t , 939 (1979)
92%
224
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 1 4 2
Me1 or I2
>go%
CHCl 3 , 1 8 - c r o w n - 6
Br
Br T e t r L e t t , 3519 (1977)
0
II
Me-C-O-CH2 Ph’
c= c’
C1 COOEt
\
‘CH2NEt2
0 II Me-C-O-CH \ 2 H, Ph°C=CLCH2C1
91%
S y n t h e s i s , 786 ( 1 9 7 7 )
30% Angew I n t E d 16, 8 5 4 (1977) KHF2, H20 Ph2CN2
*
Ph2CHF
Bu4NC104, CH2C12 T e t r L e t t , 1447 ( 1 9 7 7 )
60%
SECTION 144
S e c t i o n 143
HALIDES FROM ETHERS
22 5
H a l i d e s and S u l f o n a t e s f r o m E s t e r s and Epoxides
No a d d i t i o n a l examples
S e c t i o n 144
H a l i d e s from E t h e r s
0-
1 ) Me3SiSiMe3/12
OEt
98% 2) H20 18, 612 (1979) Angew I n t Ed -
HBr
-n-C16H33-OCH3
R4PBr
n-C
H
- 16 33
Br
88%
S y n t h e s i s , 771 (1978)
do-&, C1
Br
Br
Chem L e t t , 891 (1977)
87%
226
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Q
Et
I
SECTION 145
I
P-n
v-
I
Et4NC1 , E t 3 N
Chem L e t t , 1013 (1977) S e c t i o n 145
H a l i d e s from H a l i d e s and S u l f o n a t e s K I , Bu4PI
BuBr
Bu I
w
96%
s i l i c a g e l column
-
S y n t h e s i s , 952 (1979)
PhSbF4
Ph-CC1
91%
PhCF3
,,,
JOC (USSR) 13, 561 (1977)
N i B r 2 , Zn powder M
e
0
*
0Br KI
Chem L e t t , 191 (1978)
7 8%
227
HALIDES FROM HYDRIDES
SECTION 146
8
1) Ph2AsCH2Li
BuBr
*
79%
BuCH2Br
2 ) Br2
-
Angew I n t Ed
BuLi
76, 53
(1977)
1) Et20
+
BuS02CF3
74%
2 ) H*0
PhN ( S02CF3)2 JOC 42, 3875 (1977)
S e c t i o n 146
H a l i d e s f r o m Hydrides
a-Halogenations o f ketones, e s t e r s , and a c i d s a r e found i n S e c t i o n s 369 (Haloketones), 359 ( H a l o e s t e r s ) , and 319 ( H a l o a c i d s ) .
Me
I
Et2C-H
PhIC12
*
Me
I
Et2C-C1
Chetn L e t t , 961 (1979)
82%
228
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
‘gH1 3CH2CH3
* Fe ( I I ) , CF3COOH
JOC
44,
SECTION 146
76% ‘gH1 3fHCH3 c1
3728 (1979)
1 ) T1 (OCOCF3)3 71 %
JOC 42, 362 (1977)
Chem Ber
E, 1677 (1979)
NBS-DMF
JOC 44, 4733 (1979)
Br
SECTION 146
HALIDES FROM HYDRIDES
229
Chem L e t t , 223 (1978) DBU-BrCC1
Br
Br
99%
same c o n d i t i o n s PhCXH
+
PhC-CBr
99%
Chem L e t t , 73 (1978)
C12, hu ~50% cc14 Chem and I n d , 127 (1977)
1 ) KOH, H20
C7H15-CH2N02
*
F’
C7H15-CHN02
2) C12, CH2C12
JOC 42, 3764 (1977)
92%
230
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
4
H=CH- CMe3
SECTION 147
F
0I 1) CHJNHBr,
C=CH-CMe3 I
HF
2 ) KOH
OMe
'Q
74%
OMe
Synthesis, 217 (1978)
*
Ph-H A1 C1
Ph-SO,CF, L
J
61 %
JOC 42, 3875 (1977)
" S e l e c t i v e Halogenation of S t e r o i d s Using Attached Aryl I o d i d e Temp1 a t e s " 99, 905 (1977) JACS S e c t i o n 147
H a l i d e s from Ketones
poEt2NSF3
JCS P e r k i n I , 1354 (1 979)
up t o %go%
HALIDES FROM OLEFINS
SECTION 149
2 31
JOC 43, 4367 (1978)
S e c t i o n 148
Hal i d e s and Sul f o n a t e s f r o m N i t r i l e s
No examples
S e c t i o n 149
Halides from Olefins
For h a l o c y c l o p r o p a n a t i o n s see S e c t i o n 74 ( A l k y l s f r o m O l e f i n s )
0
1 . LiA1H4, TiC14 73%
2.
*
CUCl*
Chem L e t t , 833 (1978) CH=CH2 I
1 ) HSiC13
2) KF
P
3 ) NBS JACS
2, 290
(1978)
232
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Bu-CHZCH~ *
1. LiA1H4, Cp2Ti (A1H3I2
*
2. Br2
SECTION 149
Bu-CH2CH2Br
79%
Chem Lett, 1117 (1977)
-
44, 3872 (1979) JOC 1 ) LiA1H4, TiC14
*
rB-
J Organometal Chem
142,71
HC1 , H202 phase-transfer cat. Synthesis, 676 (1977)
(1977)
76%
HALIDES FROM MISCELLANEOUS COMPOUNDS
SECTION 150
233
60%
JOC 42, 1559 (1977)
+
cc1
c
1
~
c
c
1
3
83%
R u ( I 1 ) complex Chem L e t t , 115 (1978)
Use o f a heterogeneous s o l v e n t suspension method f o r benchtop f l u o r i n a t i o n o f a1 kenes u s i n g XeF2. T e t r L e t t , 363 (1977)
S e ct ion 150
Hal i d e s from M i s c e l l aneous Compounds
HF, p y r i d i n e Ph-N=N-NMe2
+
Ph-F
97%
JCS Chem Comm, 914 (1979) Review:
“ I n t r o d u c t i o n of F l u o r i n e i n t o Organic Molecules:
and How” Tetrahedron
34, 3
(1978)
Why
234
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 150
Review: "The Invention of Reactions Useful for the Synthesis of Specifically Fluorinated Natural Products" Pure and Appl Chem
49,
1241 (1977)
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 11
PREPARATION OF HYDRIDES T h i s chapter l i s t s hydrogenolysis and r e l a t e d r e a c t i o n s by which f u n c t i o n a l groups are replaced by hydrogen, e.g.
RCH2X
+
RCH2-H
o r R-H
Section 151
Hydrides from Acetylenes
No examples of t h e r e a c t i o n R G C R
Section 152
+
RH occur i n t h e l i t e r a t u r e .
Hydrides from Acid Halides
4
0
COCl
Pr3Si H
JCS P e r k i n I , 1137 (1979)
235
68%
236
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 153
SECTION 153
Hydrides f r o m A l c o h o l s and Phenols
T h i s s e c t i o n l i s t s examples o f t h e h y d r o g e n o l y s i s o f a l c o h o l s and phenols, ROH + RH
1 ) CH3S02C1 63% 2) e l e c t r o l y s i s , DMF, Et4NOTs
T e t r L e t t , 2157 (1979)
K, 18-crown- 6
86%
TH F
S
[I
0-C-NEt2
-
JCS Chem Comm, 1175 (1979)
Ph3SnH
n-C H O H 4 c-C,2H25SePh 12 25
fl-C,2H26
JCS Chem Comm, 41 (1978)
73%
HYDRIDES FROM ALCOHOLS AND PHENOLS
SECTION 153
H
1 -naphthyl-
I
C-OH I
Ph
NaBH4/CF3COOH
-
1-naphthyl-
237
YC - H i
97%
Ph
S y n t h e s i s , 172 (1977)
0 II C5H1 -C-NHCH20H
0
NaCNBH3
II
C5H1 -C-NHMe
86 %
T FA
Synth Comm 7, 549 (1977) Me2Si I2
P h2CHOH
Ph2CH2
7 1 )
96%
CH2C12
8 Ph-C-CHPh I
OH
1s
Me2Si I2
Ph-CCH-Ph
_7
45%
L
CH2C12
T e t r L e t t , 4941 (1979)
0 OH
II
I
Ph-C-CH-Ph
1 ) Me3SiI, CH C1 2
2
0
II Ph-C-CH2Ph
2 ) sodium t h i o s u l f a t e Synth Comm 9, 665 (1979)
95%
238
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
00
-9 00
SECTION 154
96%
JOC 44, 4813 (1979)
1 ) NaH, THF 2) C1PO(OEt)2
*
C
g
H
,
g
~
H 92%
3 ) T i " , THF
4) MeOH JOC 43, 4797 (1978)
Zn, HC1
ether
Me'o 97%
Tetrahedron 33, 511 (1977)
Also v i a Halides and Sulfonates , S e c t i o n 160 S e c t i o n 154
Hydrides from Aldehydes
No a d d i t i o n a l examples For t h e conversion RCHO Aldehydes)
-+
RMe e t c . see Section 64 ( A l k y l s from
SECTION 157
Section 155
239
HYDRIDES FROM AMINES
Hydrides from A l k y l s
bBr 90%
$fBr
JCS Perkin I , 176 (1979)
Section 156
Hydrides from Amides
N o a d d i t i o n a l examples
Section 157
Hydrides from Amines
This s e c t i o n l i s t s examples o f t h e conversion RNH2 -+ RH
NaBH3CN 91 % HMPA COOEt
COOEt
JCS Chem Comm, 1089 (1978)
240
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
6
SECTION 157
Me3C-ON0 82%
*
DMF
N02
N02
JOC 42, 3494 (1977)
NH20S03H
&cooH
72%
@OH
-
JACS 100, 341 (1978)
Ph-NHNH2
+-,
TosN3, NaOH
Ph-H
benzene/H20
40%
Et4NBr
T e t r L e t t , 3059 (1978)
84-1 00% A r = s u b s t . Ph Chem L e t t , 1051 (1979)
SECTION 158
S e ct ion 158
HYDRIDES FROM ESTERS
Hydrides from Esters
This s e c t i o n l i s t s examples of t h e r e a c t i o n s RCOOR' RCOOR'
EtOOC
-+
241
-+
RH and
R'H
COOEt
COOE t
1 ) KOH, 18-crown-6 benzene
70%
2) HC1 , 100" Synthesis, 37 (1977) OAc
I
T e t r L e t t , 613 (1979) O ,Ac
85%
Synthesis, 774 (1977)
242
Ac
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
XI
SECTION 159
Na &
40%
HMPA/ t-BuOH
JCS Chem Comm, 567 (1978)
Li H2NCH2CH2NH2
AcO
I n d i a n J Chem 188, 179 (1979)
A8 C=CH
CZC-BU
3 ) H20 JOC 42, 2650 (1977)
S e c t i o n 159
Hydrides from E t h e r s
T h i s s e c t i o n l i s t s examples o f t h e r e a c t i o n K - X - R ' X=O or S.
+
RH, where
SECTION 160
HYDRIDES FROM HALIDES AND SULFONATES
24 3
T e t r L e t t , 4679 (1979)
Zn, TMSCl
fic5Hll
Synth Corn
Section 160
7,
84%
427 (1977)
H.ydrides from Halides and Sulfonates
This s e c t i o n l i s t s t h e r e d u c t i o n o f halides and sulfonates RX+RH NaBH4, Me2S04
I
*
82 %
/\/\/\/ H
F u l l paper, many examples.
JOC 43, 2259 (1978)
244
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 160
NaBH3CN, g-BBNCN, o r p o l y m e r i c cyanoborane R-X
*
R-H
HMPA R = alkyl
x
= halide, tosylate
JOC 42, 82 (1977)
TH F
96%
JOC
Br
I C3H7-CH-C6H1
42,
L i A1 H4-CoC1
L i A1 H4-NiC1
2166 (1977)
*
0
decane
*
T e t r L e t t , 4481 (1977)
98 %
100%
SECTION 160
HYDRIDES FROM HALIDES AND SULFONATES
0 II NaOMe o r NaOCH cat. PdL4
-8
245
89%
JOC 43, 1619 (1978) T e t r L e t t , 1913 (1978)
&
NaH, t-AmONa 100%
*
DME
T e t r L e t t , 3951 (1977) Et3N*HCOOH
Ph-Br
*
Ph-H
92%
Pt/C
"& - && JOC 42, 3491 (1977)
83%
,HIOH
Br
JOC
42, 835
(1977)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
246
SECTION 160
CFh? -I
H2
BzCl
BzH
PPh3, NaOH
86%
J Organometal Chem 148, 311 (1978) 100%
JOC 43, 1557 (1978) Fe( CO)5
COOE t
73%
JOC 44, 641 (1979)
V
Ph
B
r
3
N i (CO)4
TH F
CHBr2
Ph
Chem Pharm 25, 1749 (1977)
60%
--
HYDRIDES FROM HALIDES AND SULFONATES
SECTION 160
247
COCl2
98%
LiA1H4
Br
JOC 43, 1263 (1978)
Li CuH2
-n-C 10H21 I
+ -,
100%
c-cl OH22
8 1
JOC 43, 183 (1978) I
&I
0
/
Bu3SnH
~
c1
0
/
63%
c1
JOC 44, 151 (1979)
1 ) Bu3SnH, AIBN 80%
JACS 101 , 5414 (1979)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
248
($‘1
SECTION 160
NaI, Zn
TsO
DME
H
C o l l Czech Chem Comm 44, 246 (1979)
Me
Yr
Zn, KOH Me
JOC
Br
Br
c1
43,
NaTeH EtOH
95%
3500 (1978)
axCH 74%
Synthesis, 545 (1978)
m!Cli213r
Mo(C0)6/A1203 THF JOC 44, 2568 (1979)
80%
SECTION 160
HYDRIDES FROM HALIDES AND SULFONATES
0
electrogenerated T i (111)
!! Ph/L\
p
*
CH2Br
249
58%
Ph+H3 Can J Chem 56, 2269 (1978)
polymer-bound FeH( CO)?
92%
JOC 43, 1598 (1978)
C e ( I I I ) , NaI TH F
-0””
90%
Synth Corn 9, 241 (1979)
Na I p y r i d ine SO3
.
-4
Synthesis, 59 (1979)
86%
250
COMPENDIUM
Section 161
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 164
Hydrides from Hydrides
No a d d i t i o n a l examples
S e c t i o n 162
Hydrides from Ketones
No a d d i t i o n a l examples
For t h e conversion R2C0
+
R2CH2 o r R2CHR' see Section 72 ( A l k y l s
and Methylenes from Ketones)
S e c t i o n 163
Hydrides from N i t r i l e s
L i , NH3(1 )
JOC 42, 3309 (1977)
S e c t i o n 164
Hydrides from O l e f i n s
No a d d i t i o n a l examples
80%
SECTION 165
Section 165
HYDRIDES FROM MISCELLANEOUS COMPOUNDS
251
Hydrides from Miscellaneous Compounds
Many examples (must be t e r t i a r y ) . JACS 101, 647 (1979) Na, NH3(1) R-N=C
8
0
*
+JOX
R-H
o r Na Napth
JOC
43,
2396 (1978)
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 12
PREPARATION OF KETONES Section 166
Ketones from Acetylenes
Bu-CZC-H
Hg/Nafion-H
*
E t O H , H20
0 BU - II C- CH3
90%
Synthesis, 671 (1978) Ph-Cr C-Pr
KMn04, H20
88
+ Ph-C-C-Pr CH2C1 2, Adogen Synthesis, 462 (1978)
CH3
JOC 44, 1574 (1979)
252
81 %
KETONES FROM CARBOXYLIC ACIDS AND A C ID HALIDES 253
SECTION 167
1) Et3N
Ph t
HC- C-COPh
Section 167
Chem Ber 112, 322 (1979)
Ketones from Carboxylic Acids and Acid Halides
1 ) 2 LDA 2 ) MeSSMe
COOH
3) NCS, E t O H
JACS
OH
99, 3101
(1977)
oo Chem L e t t , 49 (1978)
66%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
254
HOOC
e le c t r o ly s i s
COOH
C 6 H l 3-C\ J ( CH2)2COCH3
'gH1 3
\
*
e t h e r / w a t e r , NaOH
SECTION 167
/c=o
63%
CH3CO ( CH2 12
T e t r L e t t , 1047 (1979)
LCOO NaCl A1 C1
96%
170"
JOC
cl-(y-cl
+
44,
3724 (1979)
- p:: Nafion-H
c1
Ph-CH3 S y n t h e s i s , 672 (1978)
4
'c-c1
I
0
L
S y n t h e s i s , 54 (1977)
SECTION 167
KETONES FROM CARBOXYLIC A C I D S AND A C I D HALIDES
J Chem Research ( S )
-
0 II
THF
+ Ph-C-C1
PrMgBr
, 46
0 II Pr-C-Ph
255
(1978)
86%
T e t r L e t t , 4303 (1979)
n-C4HgMn I
+ 0
-
AL\
‘qH9
C7H15
91 %
II
n-C7H15C-C1 S y n t h e s i s , 130 (1977)
Et4Si
+ 0 II -i-Pr-C-C1
A1 C1
0
II
/c\
Et
i-Pr -
CH2C12
Synthes is , 677 ( 1377)
82%
256
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
A
0
11
1 ) Me3Si CH2A1C1
C11 H23-C-Cl
/\
*
2 ) H20
SECTION 167
'llH23
CH3
70%
J P r a k t Chem 320, 341 (1978)
0 It
0 It PhCH2CHZCCH3
Me4Sn
PhCH2CH2C-C1
99%
BzPdL2C1 JOC 44, 1613 (1979)
Bu3B, MeLi ,
8
CuCl * COD
Ph-C-C1
*
0
II
Ph-C-Bu
T e t r L e t t , 173 (1977)
A
2 C7HI5-C-C1
T e t r L e t t , 3861 (1977)
85%
--
KETONES FROM ALCOHOLS AND PHENOLS
SECTION 168
TMS
T i C1
t
CH2C1
0
257
Bu
65%
II
BU-C-C1 T e t r L e t t , 4045 (1977)
Section 168
Ketones from Alcohols and Phenols
6
Cr03 100%
poly ( v i n y l p y r i d i n e ) r e s i n JOC 43, 2618 (1978)
OH Il
f
i
Cr03/Cel it e E t 2 0 / CH2C1
+
6
Synthesis, 815 (1979)
71 %
258
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
HO
x)
SECTION 168
H2Cr04/Si02
88%
steroid
Synthesis, 534 (1978)
Bu4NHCr04 CHCl
70% 0
Synthesis, 356 (1979)
Tetr L e t t , 1601 (1978) chromic acid 76% s i l i c a gel Tetrahedron
35, 1789
(1979)
--
SECTION 168
KETONES FROM ALCOHOLS AND PHENOLS
259
KMn04
OH
96%
CuS04
JOC
44,
3446 (1979)
O0
*
BaMn04
0
90%
T e t r L e t t , 839 (1978)
Synthesis, 297 (1978) Tetrahedron 34, 1651 (1978) JOC
0 OH
43,
2480 (1978)
1 ) Me2S0, (COC1 l2 98% 2) E t 3 N
0 JOC 44, 4148 (1979)
260
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
DMSO, TFAA
SECTION 168
*
94%
R3N, CH2C12
c; OH I
/CHCH3 Ph
Synthesis, 297 (1978)
O2
, PdCl 2-NaOAc 88%
JCS Chem Comm, 157 (1977)
PdL4, K2C03 w
0 II Ph-C-CH3
95%
PhBr, DMF T e t r L e t t , 1401 (1979)
Ce+4/
Ph-fHCH3
OH
0
Br03
*
Ph-C-CH3 II
0
Synthesis, 936 (1978)
86%
SECTION 168
KETONES FROM ALCOHOLS AND PHENOLS
ooH KI, e l e c t r o l y s i s
261
59%
H20, L-BuOH
T e t r L e t t , 165 (1979)
CuCl , 02, K2C03
P h -CH- CH3
d"
phenanthroli n e
*
Ph-C-CH3 II
'd
T e t r L e t t , 1215 (1977)
doH
93%
JOC 44, 2955 (1979)
L
FeCl L
hv JOC 42, 171 (1977)
75%
262
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 168
JCS Chem Comm, 58 (1979)
HO
1 1
(Ph3BiC1)20
*
~80%
0
JCS Chem Comm, 1099 (1978)
JCS Chem Comm, 952 (1978)
CC13CH0
2'3
*
d"
Synthesis, 555 (1977)
99%
S E C TION 168
KETONES FROM ALCOHOLS AND PHENOLS
6 xi
6
5-deazaflavin
* KOH
263
82%
JCS Chem Comm, 825 (1977)
1 ) PrMgBr
chol es tanol
2) azodicarbonyl
HO
dipiperidine
0
BCS Japan 50, 2773 (1977)
OH I
DDQ, HI04
Ph-CH=CH-CH-Me
0 It Ph-CH=CH-C-Me
80%
HCl/benzene
Synthesis, 848 (1978)
Ph3CBF4 59%
I
CH2C1 T e t r L e t t , 2771 (1978)
264
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 169
1 ) MCPBA
86%
JOC 42, 2077 (1977)
88% HO OH
Ph Chem L e t t , 179 (1977)
Aldehydes f r o m A l c o h o l s and Phenols ( S e c t i o n 48)
R e l a t e d Methods:
S e c t i o n 169
Ar-CHO
- -
Ketones f r o m Aldehydes Me3Si CN
OTMS I
1) LDA, THF
Ar-CH I
CN
P /c\R Ar
2 ) RBr
3 ) H3@ A r = subst. Ph, p y r i d y l , f u r y 1 R = Me, i-Pr,
Bz Chem Ber 112, 2045 (1979)
~80%
SECTION 169
KETONES FROM ALDEHYDES
1 ) Et-CBr2Li 2 ) BuLi
265
0
*
3 ) H3@
53% S y n t h e s i s , 968 (1979)
8 ii
1) Ph-S-CHCl
BU-CHO
0
II
81 %
Bu-C-CH2C1
T e t r L e t t , 1225 (1977) Chem L e t t , 209 (1979)
1 ) (PhS)2CHLi TMEDA n-C6H1 3-CH0
0
II
*
79%
n-C6H1HC\ 3 CH2SPh
2 ) TsOH, benzene
JCS P e r k i n I , 1074 (1979)
266
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 170
-fJQzm
S e c t i o n 170
Ketones f r o m A1 k y l s
Methylenes , and Ar,yl s
0
70%
S y n t h e s i s , 144 (1979)
0
Bz Et 3NMn04
+
Ph- CH2CH2CH2CH
II
Ph-C-CH2CH2CH
Angew I n t Ed
8 8 PhSe-O-SePh
18,68
44%
and 69 (1979)
0
II
*
PhCH2Ph
90%
Ph"\Ph
T e t r L e t t , 3331 (1979) Se02 C7H1 5-CH2-CH=CH 2 -
x
C7H1 5-C-CH=CH2 t-BUOOH -
JACS 99, 5526 (1977)
61 %
SECTION 170
KETONES FROM ALKYLS, METHYLENES, AND ARYLS
267
Cr03-C5H5N AcO
AcO 87%
-
J Chem Res (S), 42 (1979)
Cr03
-n-C5H1 -CH2-CH=CH-COOMe
Ac20, HOAc
A
n-C5H1 -C-CH=CH-COOMe 86%
B u l l Chem SOC Japan
52,
T e t r L e t t , 5021 (1978)
184 (1979)
268
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL
4 SECTION 172
L i , NH3(1)
THF, t-pentanol OMe
OMe 31, 1625 (1978) Aust J Chem -
S e c t i o n 171
Ketones f r o m Amides
No a d d i t i o n a l examples
S e c t i o n 172
Ketones f r o m Amines
1 ) L-BuLi
, THF
phyx 75%
2 ) Me1
JOC 44, 3585 (1979)
SECTION 173
S e c t i o n 173
KETONES FROM ESTERS
269
Ketones f r o m E s t e r s
COOPh
6x3
K CH2N02, DMSO
*
82 %
S y n t h e s i s , 295 (1979)
Me3AI, TFA
95%
OTMS
JACS 9 9 , 4192 (1977)
270
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 174
SECTION 174
Ketones f r o m E t h e r s and Epoxides
F6
1
86%
JACS 100, 5396 (1978)
57%
JOC
$
42,
1 ) PhSeNa, E t O H 2) MCPBA, p y r
'8
3097 (1977)
JACS 99, 7601 (1977)
~80%
SECTION 175
S e c t i o n 175
271
KETONES FROM HALIDES
Ketones from H a l i d e s
72% Chem & I n d , 213 (1979)
Ph
H
ONa
Ph
Me
2)
--
0 II Ph
Me
60%
A
JCS P e r k i n I, 2493 (1979)
-
Ph-I
N i ( CO)4
t
P h - b O C l
benzene
C1-
HgCl S y n t h e s i s , 776 (1977)
90%
272
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
R
1 ) Fe(C0)5
Bu-MgBr
2 ) Me1
SECTION 175
70%
BuAC\Me
T e t r L e t t , 761 (1978)
CO, HMPA
PhI +
Me4Sn
fl
Ph-C-Me
123%
PhPd (PPh3) 21
T e t r L e t t , 2601 (1979)
2 PhCH2Br
Fe (CO) 5, NaOH
*
0
II
PhCHZ-C-CH2Ph
94%
Bu4NBr Chem L e t t , 321 (1979) 1 ) 2BuMgx
*
MeOCH2 COOMe
P Bu /‘\BU
2 ) anodic o x i d a t i o n
T e t r L e t t , 3625 (1977)
64%
SECTION 175
KETONES FROM HALIDES
273
1 ) Et2NCH2CN, LDA 2 ) LDA, R ' X
*
R- X
0
II R-C-R'
~80%
3 ) (COOH)2, H20/THF
R , R ' = 1" a l k y l T e t r L e t t , 5175 (1978)
1 ) NaOH, B u 4 N I 2) B z B r
*
TosCH2N=C
3) i-PrI
0 II
/"\ i- P r BZ
65%
-
T e t r L e t t , 4229 (1977)
@ J ,,
Hg ( O A C ) ~ , BF3-
HOAc T e t r L e t t , 1943 (1978)
Cl T e t r L e t t , 3489 (1979)
60%
274
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 176
Related methods: Ketones f r o m Ketones ( S e c t i o n 177), Aldehydes from H a l i d e s ( S e c t i o n 55)
S e c t i o n 176
Ketones f r o m Hydrides
T h i s s e c t i o n l i s t s examples o f t h e k e t o n i c groups, RH
R2CH2
-+
-t
replacement o f hydrogen by
For t h e o x i d a t i o n o f methylenes
RCOR'.
R2C0 see S e c t i o n 170 (Ketones f r o m A l k y l s and Methylenes)
8
C F3 COS02 C F3
81 %
JOC 44, 313 (1979)
C L
NaCl A1 C l ___L
170"
COOH
JOC 44, 3724 (1979)
96%
KETONES FROM KETONES
SECTION 177
275
PhCH3 t
P h2C= C=O Chem L e t t , 535 (1978)
S e ct ion 177
Ketones from Ketones
Th i s s e c t i o n contains a l k y l a t i o n s o f ketones and p r o t e c t e d ketones, ketone t r a n s p o s i t i o n s and annelations, r i n g expansions and r i n g openings, and d i m e r i z a t i o n s .
Conjugate r e d u c t i o n s and Michael
a l k y l a t i o n s of enones are l i s t e d i n Section 74 ( A l k y l s f r o m O l e f i n s ) .
For t h e p r e p a r a t i o n o f enamines from ketones see S e c t i o n 356
(hine-01 e f in)
.
TH F T e t r L e t t , 845 (1979)
276
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Me
SECTION 177
1 ) LDA 2) B(OCH2CH2)3N, DMSO Me 3) Me1 Synth Corn
1 ) Ph3CQ, DME Ph/‘\CHMe2
2) Me1
8,
9 (1978) 0 II
*
PhYC\ CMe
76%
Synth Comm 7, 137 (1977)
JOC 43, 1834 (1978) 1 ) K-0-t-Am, DMF/DME
2) BzBr 3) NH4Cl , H20
b
Synth Corn 8, 563 (1978)
77%
SECTION 177
KETONES FROM KETONES
Me I
277
Pe “Me,
Chem Ber
111, 1337
95%
(1978)
1 ) CH2=CHCH2Br
Me
82%ee
JOC 42, 1663 (1977)
O-t-Bu
I-
t-Bu-CH
-
*
\ 1) LDA 70%
2) PrBr 97%ee(S) T e t r L e t t , 573 (1978)
278
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 177
1 ) R-NH2
w 0
2 ) LDA, Me1
3) HOAc, %Ac
0
*
R = -CHBzCH,OMe
98%ee
L
8
JOC 43, 3245 (1978)
HCHO, CO
%40%
RhCl
6
Chem L e t t , 215 (1978)
I
65%
T i C1
T e t r L e t t , 1427 (1979)
0
/OCH3 h-CH=c\
COP h
[~eH(co)~l
a
PhCH2CH2CPh
EtOH
BCS Japan
51, 835
(1978)
69%
SECTION 177
KETONES FROM KETONES
279
b OTMS
-t-BuC1
41 %
TiC14
T e t r L e t t , 4183 (1977)
t-BUC1 T i C1
Angew I n t Ed
6 OTMS
85%
17,48
(1978)
PhCH2Br, AgCl O4
CH2Ph
CH2C12, BF3* Et20
*
82%
B u l l Chem SOC Japan 52, 1241 (1979)
Br I P h-CH-CH
3
ZnBr2
T e t r L e t t , 1519 (1979)
71%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
280
SECTION 177
98 %
CH2=CHCH2Br
T e t r L e t t , 3121 (1 977)
0 II 2
CH3
R
TMS-N H
w COO-TMS
30-70%
*
Angew I n t Ed 16, 251 (1977)
n
BF3 E t p O
o r Na/NH3
66%
8 413 (1978) Synth Comm -
Chem L e t t , 231 (1978)
L
SECTION 177
KETONES FROM KETONES
281
d"
Also works w i t h s ty re n e e t c , JACS 100, 1791 and 1799 (1978)
1 ) LDA, THF Ph-CH-CN I NMe2
*
fi
Ph-C-CH2-BU
63%
2 ) BuBr
Synthesis, 127 (1979)
Review:
"Synthesis o f Aldehydes, Ketones, and Carboxyl i c Acids
from Lower Carbonyl Compounds by C-C Coupling Reactions" Synthesis, 633 (1979)
Ketones may a l s o be a l k y l a t e d and homologated v i a o l e f i n i c ketones (Section 374) Related methods:
Aldehydes from Aldehydes (Section 49)
282
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 178
SECTION 179
Ketones f r o m N i t r i l e s
No a d d i t i o n a l exampl es S e c t i o n 179
Ketones f r o m O l e f i n s
1 ) LiA1H4, TiC14
2)
.pyCH3
*
C8H1
18
54%
7-C-CH3
0
Chem L e t t , 167 (1979)
1 ) LiA1H4, TiC14
*
B U- CH=CH2
0 \I BuCH2CH2C-Ph
71%
2 ) PhCOCl Chem L e t t , 623 (1979)
I n d i a n J Chem
E, 704
(1976)
SECTION 179
KETONES FRON OLEFINS
283
b
PdCl 2-CUC1
*
75%
JCS Chem Corn, 583 (1977)
T e t r L e t t , 1827 (1977)
JOC
hv,
42,
4268 (1977)
o2 40%
p y r i d i n e , FeC13 Chem L e t t , 161 (1978) See a l s o Section 134 (Ethers and Epoxides from O l e f i n s ) and Section 174 (Ketones from Ethers and Epoxides).
284
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 180
SECTION 180
Ketones f r o m Miscellaneous Compounds
Conjugate r e d u c t i o n s and r e d u c t i v e a1 k y l a t i o n s o f enones are l i s t e d i n Section 74 ( A l k y l s from O l e f i n s ) .
6
NO,
basic s i l i c a gel 99% ether JACS 99, 3861 (1977)
1 ) L-BuOK
82 %
*+
2) t-BUOOH VO( acac)2, benzene
Ll
T e t r L e t t , 331 (1977)
1 ) NaOH, MeOH
+
JOC 43, 1271 (1978)
66%
SECTION 180
KETONES
FROM MISCELLANEOUS COMPOUNDS
(yN3
285
Na2S, E t 3 N
85%
JOC 44, 4712 (1979)
-)q 'yo i -Bu
Ph
a
1)
)-c
~50%
2)
H20
3)
Pb(OAc)4, HMPT/TH 17, 450 (1978) Angew I n t Ed -
Me I II I
Me 0
N-c-cH\ 2 H 2 ) 8
97%
p H 2 0 T e t r L e t t , 4487 (1979)
286
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1)
NaH, DMF
3)
AcOH
SECTION 180
88%
*
JOC 44, 4 5 9 7 ( 1 9 7 9 )
Ra -N i
Chem L e t t , 4 2 3 (1977)
T e t r L e t t , 1 8 9 3 (1979)
SECTION 180A
S e ct ion 180A
PROTECTION OF KETONES
287
P r o t e c t i o n o f Ketones
See Section 367 (Eth e r-Ol e fi n ) f o r t h e formation o f enol e t h e r s . Many o f t h e methods i n Section 60A ( P r o t e c t i o n o f Aldehydes) are a1 so appl i c a b l e t o ketones.
HC(OMe)3 w
montmori 11o n i t e
Meo6 97%
Synthesis, 467 (1977)
- togoE HC( O E t )
65%
graphite bisulfate
8
BSC France, 499 (1977)
* CHCl
T e t r L e t t , 4175 (1977)
90%
288
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4 SECTION 180A
0
A
HOCH2CH20H/THF
II
R
*
Amberlyst 15
R'
n
0 \C/O
I\ R '
R
JCS Perkin I , 158 (1979) HOCH2CH20H , benzene
92%
Synthesis, 724 (1979)
n
8
wet s i l i c a gel
*
8
65%
Synthesis, 63 (1978)
MeSSMe
0
R
? / \
__L
R'
Bu3P
MeS
\ /SMe
R YC\R'
Chem Lett, 767 (1979)
SECTION 180A
PROTECTION OF KETONES
289
EtSH, Me3SiC1
100%
CHCl Synth Corn 7, 283 (1977)
Tetr Lett, 675 (1978)
8
6
Chem Pharm Bull 27, 538 (1979)
hu, Ph2C0 ,02
hexane
JCS Chem Comm, 680 (1977)
65%
290
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4 SECTION 180A
Synthesis, 720 (1979) e 1ec troc hemi c a1 ox i d a t i on
h
L i C1 O4
THF/H20,
xi
0
JCS Chem Comm, 255 (1978)
JCS Chem Comm, 751 (1977)
1)
s\c/
S
I\
R'
R
NPor N&
L
* R
i)l A R'
Synthesis, 273 (1979)
%5D%
SECTION 180A
PROTECTION OF KETONES
291
Chem Pharm 26, 3743 (1978)
Synth Comm 9, 301 (1979)
Synthesis, 877 (1979)
02’ hv
59% methyl ene blue
Synthesis, 893 (1977)
292
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4 SECTION 180A
76%
t
S y n t h e s i s , 212 (1978)
x
HON
1 ) NOCl
, pyridine
2) H20, r e f l u x
-x
81%
0
Chem and I n d , 454 (1977)
NOCl
0
*
II R
~80% R'
I n d i a n J Chem 158, 578 (1977)
e l e c t r o g e n e r a t e d T i (111)
NOH
II Ph
CH3
*
0 II
/\
80%
Ph
CH3
Can J Chem 56, 2269 (1978)
SECTION 180A
PROTECTION OF KETONES
293
T i tanous c h l o r i d e dioxane
HON
6
NNHts
Chem and Ind, 742 (1977) B r 2 , CH2C12
NaHC03, H20
-8
81 %
B r 2 , CH2C12
69% NaHC03, H20/HMPT
Synthesis, 113 (1979) ,,,/NHTs
Synthesis, 308 (1979) NNHTs NaN02, CF3COOH R
R'
0
*
II
R
Synthesis, 207 (1979)
R'
294
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4 SECTION 180A
6
d
NNHTs
95%
100, 5396 (1978) JACS -
R
>c= N -NH T ~
R'
Synthesis, 919 (1978) NNHTs
II
R
/"\
R'
CuS04, H20
*
MeOH, THF
v
0
/\ R
%go% R'
Gazz Chim Ital 108, 137 (1978) NNTs
II R
T1 (OAc)3
0
II
_ L
R'
HOAc
R
Tetr Lett, 4583 (1979)
R'
PROTECTION OF KETONES
SECTION 180A
Hydrazones
( PhSeO) 2O
Oximes Semicarbazones
6
t
295
Ketones
JCS Chem Comm, 445 (1977)
CO (CO
PhMe2SiH
l8
OSi Me2P h 85%
PYr
T e t r L e t t , 2671 (1977)
0
g S i Me3 Me3SiI , HN(SiMe3)2
81% CH2C1
6-
S y n t h e s i s , 730 (1979)
6,,,
PhS-TMS
JACS
99, 5009
(1977)
296
COMPENDIUM
OF ORGANIC S Y N T H E T I C METHODS VOL 4 SECTION 180A
S e l e c t i v e formation o f enolate i o n s t o p r o t e c t carbonyl groups from r e d u c t i o n by LiA1H4.
Used t o e f f e c t s e l e c t i v e reductions o f
s t e r o i d diones and t r i o n e s .
JCS Perkin I , 1075 (1977)
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 13
PREPARATION OF NITRILES S e c t i o n 181
N i t r i l e s from Acetylenes
[ N i ( CN),I2PhCH2CH2CzCH
0
CN, NaBH4
PhCH CH CHCH3 2 21 CN
92%
JCS Chem Corn, 1110 (1979)
Section 182
N i t r i l e s from Carboxylic Acids and Acid Halides
No addi t i onal examples
S e c t i o n 183
N i t r i l e s from Alcohols
No a d d i t i o n a l examples
297
298
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 184
SECTION 184
Nitriles from Aldehydes 1 ) (i-Pr)3PhS02NHNH2
*
CgH1 3-CH0
2) v
C H -CZN 6 13
92%
Synthesis, 112 (1979)
63% Synthesis,703 (1978)
1 ) NH20H*HC1 Pyrid ine/CHC1
R-CHO
2) Se02
R = a1 kyl ,
P
R-CN
%80%
a w l , heterocycl ic Synthesis, 722 (1979)
Ph -CH=N -OH
+ -'
TFAA py r id i ne
Ph - CZN
Synthesis, 56 (1979)
90%
SECTION 184
NITRI LES FROM ALDEHYDES
n-C6H13-CH=NOH -
Et3N
299
C H -CzN 6 13
83%
Synthesis, 702 (1978)
C1S02NC0
C5H1 1-CH=NOH
C5H1 -CN
75%
Et3N
Synthesis, 227 (1979)
Q
CH=NOH Me-C:C-NEt2
*
CH3CN
No2
Ph -CH=NOH
80% N02
Synthesis, 338 (1977)
@-PPh2*CC14
*
Ph-C-N
Synthesis, 41 (1977)
76%
COMPENEIUM OF ORGANIC SYNTHETIC METHODS VOL 4
300
SECTION 184
P2IqY pyridine
*
n-C7H, 5-CH=NOH
C7H1 5-C=N
64%
Synthesis, 905 (1978) Ph
*
NH2
Ph-CHO
2)
Ph-CN
99%
A
JCS P e r k i n
y
1957 ( 379)
n i c k e l peroxide
+
Ph-CHO
Ph-CN
73%
NH3, benzene, Na2S04 Synth Corn
I
HN-NMe2CH2CHCH3 C
H
Et
O
(1979)
OH
08
T
zy529
_ L
ycN
Me2CHOH Synthesis, 301 (1978)
76%
Et
NITRILES FROM AMIDES
SECTION 186
1 ) (i--Pr)3PhS02NHNH2 C6Hl 3-CH0
301
*
C6HI3CH2CN
72%
2) KCN, MeOH JCS Chem Corn, 280 (1977)
Section 185
N i t r i l e s from Alkyls. Methylenes and Ar-yls
No a d d i t i o n a l examples Section 186
N i t r i l e s from Amides
A n-C1 7H35-C-NH2
-
@-PPh2
eCC1
n-C, 7H35-CzN
Synthesis, 41 (1977)
T e t r L e t t , 1813 (1977)
100%
302
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S Ph-C-NH2 I1
N-COOEt N-COOE t
SECTION 186
I1
T
Ph3P
Ph-C-N
59%
JCS Chem Corn, 220 (1977) JOC 44, 3436 (1979)
R
BZ - C- NH2
C1S02NC0 Et3N
Bz-CN
84%
Synthesis , 227 (1979)
CH3CH2-NH-CH0
bismuth phosphomol y b d a t e 02, 400-500"
*
CH3CH2CN
90%
Chem & Ind, 852 (1979)
ISI
Ph-C-NH2
BrCH2CN %Et
Ph-CgN
Synth Corn 9 , 569 (1979)
85%
SECTION 190
Section 187
NITRILES FROM HALIDES
303
N i t r i l e s from Amines -___-_CUCl
Ph-CH2NH2
y
o2
p y r id ine
*
Ph-CGN
35%
Synthesis, 245 (1977)
Section 188
Y i_L r i l e s from E s t e r s
0 II
Me2A1NH2
R-C-OR'
R = alkyl
xylene , A
*
R-CN
, aryl T e t r L e t t , 4907 (1979)
Section 189
N i t r i l e s from E t h e r s a n d Epoxides
No a d d i t i o n a l examples
Section 190
N i t r i l e s from Halides
HMPA
JOC 43, 1017 (1978)
%70%
304
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 190
NaCN (on alumina) M
B
b
r
m
C
N
93%
JOC 44, 2029 (1979)
JOC 44, 3436 (1979) Et4NCN
wBr v
mcN 80%
CH2C1
L i e b i g s Ann Chem, 1946 (1978)
Bux KCN, PdL4
Br
*
Bu
%CN
crown e t h e r , benzene
T e t r L e t t , 4429 (1977)
NaCN , a1 umi na Pd(I1) c a t a l y s t
JOC -_ 44, 4443 (1979)
96%
SECTION 191
305
NITRILES FROM HYDRIDES
1 ) 1-pentyl-ONO, HC1 2) NaN3, DMF 560% overall Synthesis, 102 (1979) Section 191
Nitriles from Hydrides-
_ i _
1 ) DMF acetal 2) H2N-OS03H
Q
CH2CN
*
N02
N02
Tetr L e t t , 1361 (1979)
$N
BrCN
A1C13, CS2 35, 2927 (1979) Tetrahedron -
64%
306
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 192
SECTION 193
N i t r i l e s from Ketones
___.___
1 ) (I-Pr)3PhS02NHNH2 71 % 2) KCN, MeOH JCS Chem Comm, 280 (1977)
C= N- C H 2 T ~ 80% t-BuOK
JOC
S e c t i o n 193
42,
3114 (1977)
N e - r i l e s from N i t r i l e s -____-_____-
Conjugate r e d u c t i o n s and Michael a l k y l a t i o n s o f o l e f i n i c n i t r i l e s a r e found i n S e c t i o n 74 ( A l k y l s from O l e f i n s ) .
1 ) Bu [ CuBrIMgC1
Ph-CZC-CN
v 2 ) H30
Ph
\
/C=CHCN Bu (cis)
Synthesis, 454 (1978)
96%
SECTION 195
NITRILES FROM MISCELLANEOUS COMPOUNDS
307
Synthesis, 430 (1979)
Section 194
N i t r i l e s from O l e f i ns
J4
OH I Me2CCN, KCN
0
18-crown-6 benzene
0
CN
I
86*
T e t r L e t t , 1117 (1977)
Section 195
N i tri 1es from _- M i scel 1aneous Compounds
Et3N/S02
C6Hi3-CH2-NO2
C 6H13-C=N
CH2C1
Synthesis , 36 (1979)
78%
308
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
'2'4
SECTION 195
78%
Tetr Lett, 3995 (1979)
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 14
PREPARATION OF OLEFINS Section 196
O l ef i ns from Acetylenes -
- 4 Yb, N H 3 ( 1 )
C H C-C-C3H7 3 7-
C3H7
85%
C3H7
JOC 43, 4555 (1978)
1 ) LiA1H4
Bu-C:C-(CH
2 ) 6 -OH
2 ) H20
Bu
\ c=c /H
H
S y n t h e s i s , 561 (1977)
309
93%
310
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
P h- CECH
1 ) (Sia)2BH
SECTION 196
*
2) Pd(OAcI2, Et3N, THF JCS Chem Corn, 852 (1977)
C6H1 3-C-C-Et
1 ) Sia2BH
2) Et3N, THF Pd(OAc)*
‘gH1 3
Et
\=/
70%
JCS Chem Corn, 702 (1978)
HC-C-C 6H 13
Li A1 H4-Ni C1
*
H2C=CH-C6H1
Tetr Lett, 4481 (1977)
96%
SECTION 196
Me
Me
1 ) DIBAH
\ / 02
31 1
OLEFINS FROM ACETYLENES
96%
\ N-CH~-CH;CHQ
/
BZ
(IT stereochem)
T e t r L e t t , 3145 (1979)
C H CZC-C H 3 73 7
Et I
il C
EI t
HZ
90%
b
C3H7
polymer-bound PdC12
HE, NaH, Ni(OAc)z
98% /7 Et Et
+
THF/E t O H
T e t r L e t t , 3955 (1977)
L i A1 H4
CH3-C-C-Pr
NiClz
H
\
/H
CH3 /c=c\
JOC 43, 2567 (1978)
92%
Pr
312
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
c+
MgH2 CH3-C:C-C
SECTION 196
/3H7
z
H 3 7
81 %
/"="\ H
CU -0- t -Bu
H
JOC 43, 757 (1978) I
-
H
\
1 . BuCECH
(C6H11)2BH
2. PhI(OAc)2
Iu
'sHl /c=c\1
60%
H
Chem L e t t , 665 (1978)
BU
''=c'qoxl
\
PhI
/H
H
NaOEt, Pd$ benzene
0
H
Bu)=( H
Ph
100%
JCS Chem Comm, 866 (1979) Me 1) C7H1 5-CrCH
CH2ZnBr
*
BSC France, 1173 (1976)
72%
31 3
OLEFINS FROM ACETYLENES
SECTION 196
T e t r L e t t , 1363 (1978)
1) Me3A1 -C1 2ZrCp2 PhC-CD 2)
Ph
*
Hp
\
/D
Me/"="\
98% H
JACS 100, 2252 (1978)
OH
CzCH
H2C=0, CuBr
&CH=C=CH2
OH
97%
i-Pr2NH, dioxane JCS Chem Comm, 859 (1979)
Review: "The S e l e c t i v e Hydrogenation o f T r i p l e Bonds w i t h Organometall i c T r a n s i t i o n Metal Compounds" Pure and Appl Chem 50, 941 (1978)
314
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 197
SECTION 198
Olefins. f r o m C a r b o x y l i c Acids and A c i d H a l i d e s
No a d d i t i o n a l examples
S e c t i o n 198
O l e f i n s f r o m A l c o h o-ls
FeCl 90%
s i l i c a gel JOC 43, 1020 (1978)
%40-80%
JOC 44, 1221 (1979)
DMPADC*
*
-N, -N -
*d m
72%
Dimethylphosphoramidic d i c h l o r i d e
Chem L e t t , 923 (1978)
SECTION 198
OLEFINS FROM ALCOHOLS
315
Acta Chem Scand (6) 31, 721 (1977)
0 Ph
OeN Et3N
74%
JACS 100, 5981 (1978) TiC13/K
0-0
85%
JOC 43, 3255 (1978) Me
OH JOC 42, 1317 (1977)
316
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 198
1 ) Me2NCH(OMe)2 2) Me1
0:::; 3 ) toluene, r f x .
T e t r L e t t , 737 (1978)
Examples u s i n g carbohydrates JCS Chem Cow, 866 (1977) JCS Perkin I,2378 (1979)
Chem L e t t , 413 (1978)
90%
SECTION 199
OLEFINS FROM ALDEHYDES
CH2SPh
H o w c t r o l y s i s
DMF, TsOH
w
T e t r L e t t , 2807 (1978)
Section 199
31 7
O l e f i n s from Aldehydes
JOC 43, 790 (1978)
I n d i a n J Chem 15B, 290 (1977)
92%
318
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 199
0
II ( Et0)2PCH2X
Ph-CHO
PhCH=CHX
90-98%
KOH, THF
X = CN, COOEt Synthesis, 884 (1979)
Ph3P=CHC1 81%
Ph-CHO
JCS Chem Comn, 446 (1978)
( Me2N)3P=CC12 C5H1, CHO
*
C5H1 1CH=CC12
T e t r L e t t , 1239 (1977)
T e t r L e t t , 2417 (1978)
94%
SECTION 199
31 9
OLEFINS FROM ALDEHYDES
-
PhCH2CH2CH=NNHTs t
PhCH2CH2CH=CHEt
70%
E t CH ( L i ) CN JACS 101 , 249 (1979)
PhCHO
t
oq SCOOEt
-*,
0
84% Chem L e t t , 197 (1978)
T i C1 3/K
M
C
H
O
C4HgCH=CHC4Hg
77%
-
JOC 43, 3255 (1978:
2 Ph-CHO
WC16, LiA1H4
JOC
b
43,
/dPh 73% Ph 2477 (1978)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
320
SECTION 200
0 NMe I\ JJ 1 ) Ph-S-Me
THF, Ph3CH, B u L i CH3( CH2) 8CH0
56%
CH3( CH2)&H=CH2
b
2 ) A1/Hg THF/H20/HOAc JACS 101, 3602 (1979)
S e c t i o n 200
O l e f i n s f r o m A l k y l s , Methylenes and A r y l s
T h i s s e c t i o n c o n t a i n s dehydrogenations t o f o r m o l e f i n s and u n s a t u r a t e d ketones, e s t e r s , and amides.
It also includes t h e
reduction o f aromatic r i n g s t o o l e f i n s .
Hydrogenation o f a r y l s t o alkanes and dehydrogenations t o f r o m a r y l s a r e i n c l u d e d i n S e c t i o n 74 (A1 k y l s , Methylenes, and A r y l s f r o m O l e f i n s ) .
t-BuOH , PdCl HC1 , 80"
*
I
80%
S y n t h e s i s , 773 (1977)
0
\I
( PhSe) 2O
0
JCS Chem Comm, 130 (1978)
39-92%
OLEFINS FROM ALKYLS, METHYLENES, AND ARYLS
SECTION 200
C-NMe2
1 ) C0Cl2
32 1
C-NMe2
‘’Q
70%
Meow , Et3N
J.
0
JACS 101 , 4381 (1979)
r
Me0
I*, D M S O / H ~ S O ~
0
Me0
0
%loo% Chem & I n d , 315 (1979) C3H7
5--
DDQ dioxane
C3H7
N ,
0
&C6H,
89%
‘gH1 3
80
J Chem Res ( S )
, 311 (1979)
, CF3COOH2NMePh 0 8 b
THF T e t r L e t t , 2111 (1978)
90%
322
M
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Mefy -
e OTM6S Z n / C u , CH212
H2°C:isOq
C1 CH20CH3
A
JACS
Me I Et-CH-CH2CH ( O E t ) 2
101,984
Me2NH*HC1
*
Me SECTION 200
(1979)
Me I Et-CH-C-CHO
HCHO
II CH2
82%
J Chem Research ( S ) , 262 (1978)
43, 4555 (1978) JOC -
SECTION 203
Ca, CH3NH2
*
JOC
Related methods: 65)
6
OLEFINS FROM ESTERS
44,
323
85%
3737 (1979)
A l k y l s and A r y l s from A l k y l s and A r y l s (Section
A l k y l s and Aryls from O l e f i n s ( S e c t i o n 74)
S e c t i o n 201
O l e f i n s from Amides
No a d d i t i o n a l examples
S e c t i o n 202
O l e f i n s from Amines
cN+
1 ) CF3S03CH2COOEt 2) DBU
*
EtOOC&
tOOEt
(64:36 E : Z ) T e t r L e t t 1241 (1977) S e c t i o n 203
O l e f i n s from
Esters
N02 Also works w i t h lactones.
Chem L e t t , 189 (1977)
89%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
324
SECTION 204
1. TsCH,MgI L
2. NaBH4 63% 3. E l e c t r o c h e m i c a l r e d u c t ion
COOMe
k
'6
Chem L e t t , 69 (1978)
0 80
COOMe
4 Ph3P-CH2
C' H
0
S OCH
CH2
DMSO
JOC
S e c t i o n 204
H\ Bu
/c-c,
78%
44,
3157 (1979)
O l e f i n s f r o m Epoxides
NaI , TFAA
/"\ H, Bu
CH3CN, THF
H
* Bu/c=c\u
JOC 43, 1841 (1978)
95%
OLEFINS FROM EPOXIDES
SECTION 204
P214, pyridine
*
325
/J
95%
Synthesis, 905 (1978)
A
n-C 8H17 -
p13
A
n-'8"17
1> M
=
Nouveau J Chem
2, 705
MeP(OPh)31 BF3*Et20
*
(1979)
p
JOC 43, 2076 (1978)
No, W , Ti, Zr
83%
JCS Chem Comm, 99 (1978)
%go%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
326
SECTION 204
Do 0
II
( EtO)pP-TeNa
88%
JCS Chem Comm, 658 (1977)
Do
T i C13 , L i A1 H4
0
*
0 0:: TiC13, LiA1H4
*
JOC 43, 3249 (1978)
Fe ( CO ) 4TMU
* 0
0
TMU = t e t r a m e t h y l u r e a T e t r L e t t , 4155 (1977)
69%
96%
OLEFINS FROM HALIDES AND SULFONATES
SECTION 205
-
327
1) HBr
‘gH1 *TMs 3
H
2) BF3*Et20
85% Br
‘sHl 3
JACS 99, 1993 (1977)
S e c t i o n 205
___Olefins
6
from H a l i d e s and S u l f o n a t e s
t-BuOK/pet.
ether
+
18-crown-6
0
S y n t h e s i s , 372 (1979)
Angew I n t Ed
16,44
(1977)
83%
328
6
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
6
8 0
1) CH2=NMe21
*
2 ) H202
3) 150"
SECTION 205
~80%
T e t r L e t t , 1299 (1977)
Me0 92%
CH2 I
R = -CX-CMe20Me JOC 43, 3418 (1978)
CH2=CH2
Me
, Et3N
*
Pd( OAc)2L2
JOC 43 , 2454 (1978)
OTHP
SECTION 205
OLEFINS FROM HALIDES AND SULFONATES
1) MeLi, CuI
*
('sH1 3)3B
C7H14-CH=CH2
329
53%
2) & B r BCS Japan 50, 2199 (1977)
1 ) BuLi CH2= CHSeP h
*
2, !!.-CIOH1lBr
\
H
,ClOH11 80%
Bu/="\
3) 03, ( i - P r ) 2 N H JOC 43, 4252 (1978)
I
3 ) toluene, r f x T e t r L e t t , 4917 (1978)
T e t r L e t t , 323 (1978)
H
330
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 205
NaHTe
76%
EtOH
Synthesis, 311 (1978)
VCl,/LiA1H4 PhCH=CHPh
97%
THF Synthesis , 170 (1977)
A1203, 25" Et20
-Q
81 %
JOC --42, 3173 (1977)
CH3 ( CH2) 7-iH-CH2TMS S02Ph
-
CH3(CH2)7-CH=CH2
T e t r L e t t , 2649 (1979)
80%
OLEFINS FROM KETONES
SECTION 207
P
‘gH1 7
-
S02Ph
sugar
‘gK
CgH1 7CH=CHMe
JCS P e r k i n I , 123 (1977)
Na
THF
Chem Pharm 25, 2134 (1977)
S e c t i o n 206
O l e f i n s f r o m Hydrides -
No a d d i t i o n a l examples
S e c t i o n 207
77%
TH F
1 TOMsm, .‘OMS
331
O l e f i n s f r o m Ketones
T e t r L e t t , 2417 (1978)
~65% -
332
COMPENDIUM
6
OF ORGANIC SYNTHETIC METHODS VOL 4
Cp2Ti CH2A1 C1( CD3)2 b
SECTION 207
65%
JACS 100, 3611 (1978)
C1 CH2Si Me3
Ph2C=0
Ph2 C= CH2
78%
Ph3P
JOC 44, 413 (1979)
16, 862 (1977) Angew I n t Ed -
NMe
II
1 ) Ph-S-Me, THF, II 0 Ph3CH, BuLi
-6
45%
2) THF/H20/AcOH
JACS 101 , 3602 (1979)
SECTION 217
OLEFINS FROM KETONES
333
JCS Chem Comm, 446 (1978)
0 I1 ( Et0)2PCH2CN
Ph
\
1
Ph
Me
/"=
KOH, THF
Me
88% CN
Synthesis, 884 (1979)
T i C1 3/3Li
79%
JOC 43, 3255 (1978) Ph
TiCl3/LiA1H4
~50% Ph Ph
r i n g s i z e 3-12 JOC 43, 3609 (1978)
334
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
n
=
2-14
0 II
2 C3H7-C-Me
JOC
42,
TiC12, pyridine
*
THF/dioxane
SECTION 207
2655 (1977) Me
Me
\ I C3 7
H -C=C-C3H7
61%
Synthesis, 553 (1977)
NNHTs Ph +ph
&-.'
L DA
TMEDA
P
h
T Ph
66%
JOC 43, 1404 (1978) 1 ) EtMgBr ___)
2) Li JCS Chem Comm, 847 (1978)
87%
SECTION 208
OLEFINS FROM NITRILES
OPO( OEt)2
brH3
1 ) Active T i
*
2) EtOH
335
OcH3 83%
JOC 43, 2715 (1978)
~80%
2) base
TMS
B u l l Chem SOC Japan 52, 1760 (1979)
Related methods:
Section 208
O l e f i n s from Aldehydes, Section 199.
O l e f i n s from Nitriles
NaClOH8
CN
HMPA
JOC 44, 2994 (1979)
90%
336
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
PhCH2CH2CH=NNHTs t
-
PhCH2CH2CH=CHEt
SECTION 209
70%
E t C H ( L i ) CN
-
JACS 101 , 249 (1979)
1 ) NaNH2, benzene 79 %
T e t r L e t t , 3187 (1977)
S e c t i o n 209
-fins
from O l e f i n s
Me3A1, CH2C12 C8H1 7-CH=CH2
Cp2Ti C1
*
‘gH1 7
\
/c=CH2 Me
JOC 44, 3603 (1979)
74%
SECTION 210 Section 210
OLEFINS FROM MISCELLANEOUS COMPOUNDS
337
Olefins from Miscellaneous Compounds
a-H - (7) Me2S04
53%
A
JACS 99, 1172 (1977)
P h2C=CHN02
Na2S, PhSH
*
DMF
Ph2C=CH2
94%
Tetr Lett, 1733 (1979) YO2 Me- CH2CH2COOMe
e-I
Me-;-CH2CH2COOMe
Me *-
,I#-
La/ ng T
NO2
CH CH COOMe
\ / 2
'C 84% II C / \ I \ CH,CLI H2COOMe Me
JOC 42, 2944 (1977) BF3 Et20 100"
C ~ -CH=CHCH~ H ~ 88%
Synthesis, 717 (1977)
338
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Co2 ( co l8
Ph C=S 2
SECTION 210A
Ph2C=CPh2
71 %
JOC 42, 3522 (1977)
S e c t i o n 21 OA
L r o t e c t i o n o f 0 1 e f ins -
A1C13, CS2
bBr
*
90%
Use o f t h e t - b u t y l group t o b l o c k p o s i t i o n s on an a r o m a t i c r i n g . I
JCS P e r k i n I , 176 (1979)
Br
1) B r 2
@ B
THF o r CHC13
r
62%
75% Br
Synthesis, 964 and 966 (1979)
SECTION 210A
PROTECTION OF OLEFINS
Review: "Selective Synthesis o f Aromatic Compounds Using Pos it i onal Pro t e c t i ve Groups " Synthesis, 921 (1979)
339
Compendium of Organic Synthetic Methods, Volume4 Edited by Leroy G. Wade, Jr. Copyright 0 1980 by John Wiley & Sons, Inc.
CHAPTER 15
PREPARATION OF DIFUNCTIONAL COMPOUNDS S e c t i o n 300
Acetylene - Acetylene -
HCE C-CH20Ts
Bu-CEC-MgBr
Bu-CzC-CH2-C=CH
75%
CuBr/THF
S y n t h e s i s , 292 (1979)
Sect on 301
Acetylene
-
Carboxylic Acid
. -
No a d i t i onal examples S e c t i o n 302
Acetylene - Alcohol
0 It
Me-CEC-C-i-Bu -
LiA1H4
Darvon
H &-CzC--(---OH i-Bu -
94% 82%ee
JACS 99, 8339 (1977) 340
SECTION 302
ACETYLENE
ALCOHOL
c h i r a l LAH complex
0 II t-Bu-C-CECH
*
-
341
*
*
*
t-Bu-CH-CXH
90%ee
AH [ L i A1 H4, ti--methylephedrine,
3,5-dimethyl phenol]
T e t r L e t t , 2683 (1979)
1 ) 9-BBN C6H, $zCCH2C=CH2
I
CH3
2) H202,
0
*
98 I C6Hl 3C~CCli2CHCH20H
I
OH
CH3
JOC 44, 2328 (1979)
1 ) LiNH2, NH3
H-C:C-CH2CH20H
Bu-CZC-CH~CH~OH
2) BuBr
H e l v Chim Acta
61,2275
(1978)
72%
342
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
( CH2C-C)Li2
1) BuBr
*
SECTION 302
BuCH2CsCCH2CH20H
66%
JCS Perkin I , 1218 (1979)
-
r \
2 ) NaOH, H202
OH
JACS 100, 5561 (1978)
PhCHO
Me S i - C X L i 3 chiral pyrrolidine catalyst
*
"f C z C-S i Me3 OH
Chem L e t t , 447 (1979)
99% 89%ee
SECTION 304
ACETYLENE
Section 303
Acetylene
-
CXLi
- AMIDE
343
Aldeh.yde
ether
CZC-CHO
63%
t
0
H
AOET
Synthesis, 307 (1979)
1 ) BuLi, THF 2)
CUI
97%
HCs CCH ( O E t ) 2
JOC 42, 2626 (1977)
Section 304
Acetylene
No a d d i t i o n a l examples
CrCCH ( O E t )
-
Amide-
344
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 305
Acetylene -_Amine
Me, 0 II Ph-CH-C-Cl
N-CrC-SnPh
Ph’
3
*
81 %
1
Ph- H-C-CZC-N
F
I
OAc
OAc Angew I n t Ed
S e c t i o n 306
SECTION 307
Acetylene
L i [Bu3B-C=C-COOEt]
-
‘Ph
(1979)
Ester
I2
18,405
/ Me
Bu-CzC-COOEt
79%
Synthesis, 679 (1977)
Section 307
Acetylene __
OH OH
I I
-
Ether, Epoxide -_____
T s C l , NaOH
Ph-CH-CH-CECH
Ph-CH-CH-CrCH
Synthesis
, 706
(1977)
83%
ACETYLENE - KETONE
SECTION 309
S e c t i o n 308
Acetylene
-
345
Halide
1) BuLi
Ph-C-C-H
Ph-CEC-Cl
69%
2) NCS
S y n t h e s i s , 296 ( 1 979)
S e c t i o n 309
Acetylene
-
Ketone
JACS 99, 954 (1977)
8
t-Bu-C-C1
L2PdC1
t
8
t-BU-C-CSC-Ph -
CuI, E t 3 N
Ph-C-C-H Synthesis, 777 (1977)
79%
346
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 309
Bu-C-C-A1Me2 D i BAH t
71 % sC-BU
JACS 100, 2244( 1978)
CO2
W6
HBF4 Me20 86%
T e t r L e t t , 4349 (1978)
@ @
Ph3C-OCH2CH2C=C L i
+
c
THF O Ph3C-0
O
H 99%
HG+
T e t r L e t t , 937 (1978)
SECTION 310
ACETYLENE
-
NITRILE
34 7
H
T e t r L e t t , 2301 (1978)
JOC 42, 2380 (1977) S e c t i o n 310
Review :
Acetylene
-
Nitrile
"a-Cyanoacetyl enes" Russ Chem Rev
46,
374 (1977)
348
COMPENDIUM
Section 311
OF ORGANIC
SYNTHETIC METHODS VOL 4
SECTION 311
Acetylene - O l e f i n ..__I
1 ) MeLi 0DIBAL-H 92%
Synthesis , 52 (1977)
Bu-C-C-B
3)
+
Me0
85%
Bu-C-C'
JOC 42, 3106 (1977)
T e t r L e t t , 3873 (1979)
SECTION 312
Bu
\
H/c=c\I
CARBOXYLIC A C I D
C1 ZnC-C-C5H1
/H
-
CARBOXYLIC A C I D
Bu
\
*
/H
H/c=c\
PdL4
349
CzC-C
H
76%
5 11
dCS Chem Comm, 683 (1977)
0
0+ 4
THF
PhMgC1
Ph
%C-CH
76%
JCS Perkin I,2136 (1979)
Section 312
Carboxylic Acid
-
Carboxylic Acid
1) 03 2)
H2, L i n d l a r
*
C O O H 'OH
B u l l Akad USSR Chem JOC (USSR)
14,48
25,
(1978)
98%
1790 (1977)
350
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
*
K02 phase-transfer c a t .
SECTION 312
c:::; 92%
T e t r L e t t , 3689 (1978)
1 ) PhSSPh, LICA*
2) Pb(OAC)4 3) NaOH, H202
$C02H
*
4) H3@
*LICA = l i t h i u m isopropylcyclohexylamide JACS 99, 4405 (1977)
qCH3 1 ) LDA, THF
COOH
OMe
2) (MeO)$O
OMe Synthesis, 245 (1977)
63%
CARBOXYLIC ACID
SECTION 313
- ALCOHOL
6 HOOC
1) CH2(COOEt)2,
NaNH2, dioxane
6Ts
351
*
COOH 65%
2) saponification Synth Corn
Section 313
_Carboxylic Acid
0
II
Me -C-COOH
6 n-C5H1 -CHO
I,
1 (1977)
- Alcohol OH 1 Me-CH-COOH
1) (Et0I3P *
2) NaOH
94 %
JOC 42, 2797 (1977) COOH *COOL1 LiNEtp, THF JCS Perkin I , 1651 (1978)
1 ) TMS-O-CH=C(OTMS)2, SnCl
8
2 ) H30
+
&
E-C5H11 Synthesis, 27 (1979)
COOH
OH
70%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
352
SECTION 315
Rr% o&(ie+
COOH
O C O O H
R
R
H
' I CH2R I A
COOH
T e t r L e t t , 1005 (1977)
S e c t i o n 314
Carboxylic Acid
-
Aldehyde
No a d d i t i o n a l examples
S e c t i o n 315
Carboxylic Acid - Amide ____
HOCHCOOH
I
NHC-OBZ II 0 Tetrahedron
2, 467
(1978)
OH
CARBOXYLIC A C I D
SECTION 315
H2’ ( S ,S)-PPPM-Rh CH2=C-COOH
I
-
ALDEHYDE
353
*
*
CH3-CH-COOH
NHCOOCH2P I h
NHCOOCH2Ph
%go%
(R) 59%ee Chem L e t t , 777 (1977)
dooH H2
Ph
*
NHAc
Ph-CH2-CH
c h i r a l Rh phosphines
90-100%
‘NHAc 78-99%ee
JACS 99, 6262 (1977) I
T e t r L e t t , 3497 (1977)
JACS 700, 5491 (1978)
J Organometal 150, C14 (1978)
PhCH=C
\ NHAc
H2 polymer-bound c h i r a l Rh c a t a l y s t
PhCH2-CH
100%
\ NHAc 78%ee
JACS 100, 264 and 268 (1978)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
354
Related Methods:
SECTION 316
Section 316 (Acid-Amine) Section 344 ( h i d e - E s t e r ) Section 351 (Amine-Ester)
6
Section 316
Carboxvlic Acid
-
Amine FOOH
Q
CHNH2
+
CHX3
+
NH3
KOH, LiC1 , R4NC1
*
CH2C12/H20
c1
81%
c1
X = C1, B r
Synthesis, 852 (1977) Synthesis, 26 (1979)
0 II Ph-C-COONa
electrochemical r e d u c t i o n
YH2 Ph-CH-COOH
*
45%
NH40H, NH4C1, H20 Aust J Chem 31, 73 (1978) I
OY:xMe J:gMe Ac
H
I
several steps
I
RCH2
H
HC1
CH2R
I
H2N-CH-COOH
Ac
*
-90%ee T e t r L e t t , 4483 (1979)
SECTION 316
CARBOXYLIC A C I D
I
Bt-
AMINE
355
- 1 ) KOCN
R-CH-COOMe
-
R,/OOMe
HC1
CH I NHCOOMe
2) MeOH
,COOH
R
C‘ H
I
~60%
NH2
Angew I n t Ed 18, 474 (1979)
-
FH2
1 ) BzBr
Bz--- C-COOH
d
2) KOH
Me
86% 100% ee
Angew I n t Ed
-
17,117
(1978)
1 ) (i --Pr)*NET
H0
BZ
,Yo
Cllyl
2) a l l y 1 B r
Bz-C-COOH
3) HC’I/AcOH
Ph
93% 112, 128 (1979) Chem Ber 1 ) NH20H.HC1, NaOAc
~50-80% R-CH-CH2COOH
*
R- CH=CH - COOH
I
2 ) H2’ Pd/C
Synth Corn
NH2
9,
705 (1979)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
356
i-Bu
Me
1) BrCN
NBz
II
Me
2) Et3N
SECTION 316
I
@
i-Bu- C- NH3 I
74%
COOH
I n d i a n J Chem 18B, 273 (1979) 1 ) BzCl , TBABr
Me
I
Ph-CH2N=C-COOBZ
H2N-C 2 ) H2, Pd/C
Ye
-COOH
I BZ
86%
JCS P e r k i n I, 1730 (1977)
Ph2C=N-CH2CN
1 ) BzEt3NC1 50% NaOH, t o l u e n e
+
it
H2N-CH-COOH
90%
2 ) HC1 EtBr T e t r L e t t , 4625 (1978) 1 ) KOt-Bu 2) E t I
( MeS ) 2C=NCH2C02Et
Et I H2N-CH-COOH
3 ) HC03H
Liebigs Anna1 en, 2066 (1979)
81 %
-
CARBOXYLIC A C I D
SECTION 316
-i-Pr-CHO
1 ) KOH
+ CN -CH2-CONH2
AMINE
357
OH I -i-Pr-CH-CHCOOH
90%
I
2 ) HC1, H20
NH2
S y n t h e s i s , 216 (1979)
(TMS) 2NCH2COOTMS
1 ) LDA
+
2 ) HC1, MeOH
)-
Me2CH- CH- CHCOOH I bH NH2*HC1
90%
CHO JOC
CH2COOH
CHO
I
CHO
-t
i=O COOH
44,
3967 (1979)
1)
-co2
2 ) NH40H
41 % Hb
3) NaBH4
JOC 42, 3440 (1 977)
H
COOH
358
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 316
1 ) CH2=CHCN
Me
84%
Et3N, P Y ~ 2 ) Dowex (@)
Me P
C
O
O
H
HOOC
Hoocxoo" S y n t h e s i s , 150 (1979)
NNHPh
158, 573 (1977) I n d i a n J Chem -
Several methods f o r s y n t h e s i s o f 6 - s u b s t i t u t e d t r y p t o p h a n s a r e presented. JOC _-44, 3741 and 3748 (1979)
Asymmetric s y n t h e s i s o f amino a c i d s by c a t a l y t i c r e d u c t i o n o f a z a l a c t o n e s by s u b s t i t u t e d a - a c y l a m i n o a c r y l i c a c i d s .
B u l l Acad USSR Chem .27, 957, 1186, and 1190 (1978)
SECTION 317
Review:
CARBOXYLIC A C I D
-
359
ESTER
"Production and U t i l i z a t i o n o f Amino Acids" Angew I n t Ed 17, 176 (1978)
Related methods:
Section 315 ( A c i d - h i d e ) Section 344 ( h i d e - E s t e r ) Section 351 (Amine-Ester)
Section 317
Carboxylic Acid
-
Ester
EtOH/H2S04 HOOC-( CH2)4-COOH
* HOOC-(CH2)4-COOEt
~90%
continuous e x t r a c t i o n Synth Corn
MeOOC,qCOOMe
COOMe
: I$l2
2, 669
(1979)
COOMe
~
H
o
o
c
COOMe
T e t r L e t t , 1403 (1978)
~
80%
360
COMPENDIUM
S e c t i o n 318
OF ORGANIC SYNTHETIC METHODS VOL 4
Carboxvlic --
Acid
-
SECTION 319
Ether, Epoxide -_
1 ) CHC13, NaOH
54%
TH F M
C
H
O
COOH
2 ) NaOH, MeOH JOC 43, 2702 (1978) Section 319
Carboxylic Acid
-
Halide
c1
C12’ 02 >
CH3 ( CH2) 3CH2COOH
I
CH3( CH2) 3-CH-COOH
chlorosulfuric acid
92%
B u l l Chem SOC Japan 5 2 , 255 (1979)
1 ) CF2=C(SEt)2 BuMgBr
F
F I BU-CH-COOH
2 ) H20 Chem L e t t , 175 (1979)
81 %
SECTION 320
-
CARBOXYLIC A C I D
id10
L i [E t 0) P-C- COO]
96%
*
0
CHo
Ph
361
KETONE
P
h
v
C
2) H30
o
o
H
c1 Synth Corn 8, 19 (1978)
Section 320
0
C a r b o w l i c Acid
II n-C5H1 -C-C1
-
Ketone
1 ) L i CH ( COOTMS )
*
0 n-C5H,, -!-CHpCOOH
91 %
2) H20
Q n
Synthesis , 787 (1 979) Li i 1) CF2=C-OTS 2) H30Q
~68%
3) @OH
T e t r L e t t , 4809 (1978)
-
0
NaOH
0
J Prakt Chem
319, 213
CH2 CH2 CH
(1977)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
362
CN I
SECTION 322
0 II R-C-COOH
acetone
R-C= NPh
%80%
HC1 R = Subst. Ph, s t y r y l
I n d i a n J Chem 178, 169 (1979)
A l s o v i a : K e t o e s t e r s ( S e c t i o n 360)
S e c t i o n 321
Carboxylic Acid - N i t r i l e
No a d d i t i o n a l examples See a l s o :
S e c t i o n 322
S e c t i o n 361 (Cyanoesters)
C a r b o w l i c Acid
-
Olefin
Ro
0
H\ C O C O O H
1 ) ( EtO)2P-CHC00
70%
2 ) H30@
Synth Comm 8, 463 (1978)
SECTION 322
CARBOXYLIC A C I D
-
OLEFIN
363
Syn t h e s i s , 133 (1 978)
0 Me-C-( CH2)5-CH0 II
wo -
( Et o ) 2P -CH COOTMS 70%
-(CH2)5-CH=CHCOOH
A1 so works w i t h ketones. Synthesis, 131 (1978)
-COOH
*
Ph W
C
JOC 43, 5018 (1978) Also Via:
Hydroxy acids (Section 313) O l e f i n i c amides (Section 349) O l e f i n i c e s t e r s (Section 362) O l e f i n i c n i t r i l e s (Section 376)
O
O
92% H
364
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Alcohol
Section 323
-
SECTION 323
Alcohol
80% 35, 1109 (1 979) Tetrahedron -
0 -
acetone, Et4NOAc 52%
t-BUOOH, OS04
JOC 43, 2063 (1978)
Me8Sn3, hv OH
59%
benzene Tetr Lett, 2847 (1978)
L i [Bu3BCH=CH2] t
Me2CHCHO
2 ) H202, @OH
- 'B
CHMe2 OH
OH
Tetrahedron 33, 1949 (1 977)
74%
ALCOHOL - ALCOHOL
SECTION 323
365
OL i 1 Ph-CH-CH2Li t
PH
G
*
JOC
3, 4798
Ph-CH-CH
2) H30
OH I CH
2- I Et
62%
EtCHO
2 PhCH20TMS
1) t-BUOOH
(1979)
Ph-CH-CH-Ph I
2 ) NaOH, EtOH
I
69%
OH OH
0 44, 295 (1979)
Me
A Tetrahedron 33, 1945 (1977)
1) Arc,
( CH3)2C=0
//o-..
i
0 ,kHCH3
h
OH OH
\ I Me C - CH CH
JOC 43, 4255 (1978)
38%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
366
Also v i a :
SECTION 324
Hydroxyesters ( S e c t i o n 327) D i e s t e r s ( S e c t i o n 357)
S e c t i o n 324
Alcohol
( CH2)6COOMe
-
Aldehvde
CeCl
NaBH4
'CHO
JACS 101, 5848 (1979)
pH 1) RMgX
Ph
Ph-{!
R
67-82%
2) NH4C1
NPh
0
>94%ee
3 ) H30
0
(R = Me, E t , i-Pr,
vinyl)
Chem L e t t , 1253 (1978)
II 0
a CH H 2 N H P h
*
Me-C-CHO 2 ) PhMgBr
CHO /t_-Ph Me
76%
OH
3 ) H20, NH4C1 Chem L e t t , 705 (1979)
99%ee
SECTION 326
ALCOHOL
-
AMINE
367
Review: "Aldol Condensations"
F o r t s c h r i t t e der Chem Forsch Related methods:
Section 325
-
Alcohol
Alcohol
-
67,1
(1976)
Ketone (Section 330)
hide
C6F50Ac
HO-CH2CH2CH2NH2
.
-
HO-CH CH CH -NH 2 2 2 1
DMF
91 %
JCH3 0
JOC 44, 654 (1979)
Section 326
Alcohol
-
Amine
O30sN-L-Bu pyridine
0-
TsNCl Na
a::+
1% oso4 JOC 43, 2544 (1978) JOC 43, 2628 (1978)
79%
368
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 326
BuNH2 75% 2'3 JACS
99, 8208
and 8214 (1977)
HZ OMe
OMe c h i r a l Rh - f e r r o c e n y l phosphi ne
86%ee OMe
T e t r L e t t , 425 (1979)
NO I
1) t-BUN-CH2Li
<:acHo d
2) LiA1H4
N
\
t
-
3 ) Raney N i
S y n t h e s i s , 423 (1979)
-
H B
70%
u
SECTION 326
ALCOHOL
PhN-Li
I
Ph- CH- CH2 Li
-
369
PH
NHPh I Ph-CH-CH2-CH
*
8
AMINE
I CHMe2
2 ) H30
+ Me2CH - CHO
JOC
BH
44,
81 %
4798 (1979)
p y r id ine
*
PhCH2CH2CH=NOH
PhCH2CH2 CH2NHOH
92%
A1 so w o r k s w i t h oximes o f ketones, JCS P e r k i n I , 643 (1979)
NO 1 2
NHOH
H2NNH2,
Rh
I
*
QMe
77%
Tetrahedron 34, 213 (1978)
NaBH4 Ph-CH=NOH
+- ,
-i-Pr-COOH
OH I
Ph-CH2-N-CH -i- P r
2-
S y n t h e s i s , 856 (1977)
65%
370
COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 4
Section 327
Alcohol
-
SECTION 327
Ester OH
1 ) LDA -C-OMe
It
0
dCO -Me
It 0
2 ) Mo05*Py*HMPA
74%
JOC 43, 188 (1978)
7 0
1 ) LDA
OCH20Me
i-PrCHO 2) 3 ) H@
i-Pr
-
My
H
H-H 91 %
HO
(C-OCH20Me
(racemic)
o
JACS 101, 2501 (1979)
6 OH
HOAc
, H2S04
4
continuous e x t r a c t i o n
OH
T e t r L e t t , 1971 (1979)
85%
SECTION 327
ALCOHOL
-
ESTER
3 71
B u l l Chem SOC Japan
H2, EtCOOMe CH3CCH2COCH3
*
52, 1237
(1979)
OH 0 1 II CH3CHCH2COCH3
*
N i 0. t a r t a r i c a c i d
up t o 85%ee Chem L e t t , 1131 (1977) 0 II
CH2 -0- C- ( CH2)
IC-s C1
1 ) NaBH4
*
Me02C(CH2)8CH20H 67%
2) cleave, e s t e r i f y Can J Chem
56,
1562 (1978)
372
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1) e-MeC6H;’
,s
!‘CHCOO-t-Bu
-
0
SECTION 328
OH I Me---C
88 % CH2 COO-L-Bu
2 ) A1/HS
95%ee
JCS Chem Comm, 162 (1977)
Also v i a :
S e c t i o n 328
Hydroxyacids ( S e c t i o n 313)
Alcohol
-
E t h e r , Epoxide
Q OMe
OH
OH
3 ) NaOH
Can J Chem
55,
3351 (1977)
74%
S E C T I O N 328
ALCOHOL
-
ETHER, EPOXIDE
373
0 1 ;
MeOH
98%
23'
,JACS 99, 8208 and 8214 (1977) BuLi _____)
-100"
-+
64%
-78"
CH20H JOC 43, 3800 (1978) Li I 1 ) TMS-CHOMe
*
&OMe
2) C s F
b0
J C S Chem C o r n , 822 (1979)
P h3SiOOH
______)
T e t r L e t t , 4337 (1979)
77%
374
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 329
Alcohol
0
-
SECTION 329
Halide
1 ) FeC13, e t h e r 2) HO, L JOC 42, 343 (1977) L
Pd( PhCN)2C12
H %go%
benzene Several examples u s i n g s t e r o i d s .
-
JOC 44, 1569 (1979)
0
Cl I
1. Ph-S-CH3
8
C1Q
2. aq. NaHC03
Chem L e t t , 995 (1977)
98%
SECTION 330
ALCOHOL
- KETONE
375
JACS 99, 5317 (1977) Section 330
Alcohol
-
Ketone
1 ) LDA
*
H
o
~
p
h
70%
2) Mo05*Py*HMPA
JOC
43,
188 (1978)
@
CONH2
B u l l Chem SOC J a p a n 52, 1237 (1979)
376
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 330
MCPBA
81%
MeOH
OMe
Synthesis, 578 (1977)
1 ) SnC14,
ucoc1 0'' TMS -0
\
C,=
H
0
C ( OTMS )
C-CH20H
*
2 ) H30@
T e t r L e t t , 2749 (1978)
JOC 43, 1599 (1978)
71 %
SECTION 330
ALCOHOL
-
KETONE
37 7
JOC 44, 702 (1979)
8
1 ) LDA, DME
CN
3 ) H3P
Chem Ber
112,2062
(1979)
OTMS
1 ) Ph-C-$(OEt)2
0
It
OO
Ph-C-C1
0 OH
II I Ph-C-CH-Ph
2 ) @OH
Chem L e t t , 519 (1979)
77%
378
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
TMSO
x~~~~ +
H
1 ) SnC14
0 II C7H15C-C1
2)
@ H30
F1
SECTION 330
C7H15-CCH20H
90%
-co2 JOC
44,
4617 (1979)
T e t r Lett, 2345 (1978)
?I
PhCH2CH2-C-SEt
1) EtMgI
2)
B
Ph%
3 ) HgC12, CaC03, H20
Tetr L e t t , 4657 (1978)
58%
SECTION 330
ALCOHOL
-
KETONE
379
1 . NaBH4
4 CH&cH2ph 3
N \N COOET
64%
C H 03 4 CH2Ph AcOH-H20
2. HC1,
H
Chem L e t t , 245 (1977)
b
UHo Ph
(C5Hg)2B-OTf
, (i-Pr)2NEt -
______I)
PhCHO Moo5* py HMPA
73%
(96% t h r e o )
-
JACS 101 , 6120 (1979)
,OAl
CH = C 2 \
Et2
Ph
Chem L e t t , 379 (1979) 1) BuLi
2 ) Ph2C=0
Chem Ber 111 1362 (1978)
%go%
380
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Steroids
34,
SECTION 330
597 (1979)
Rev iew : "A1 do1 Condens a t ion s 'I F o r t s c h r i t t e d e r Chem Forsch 67, 1 (1976)
-n-C1
HZ3-CH2MgBr t
2 ) H30@
95% d
C
1
OH
YCN OTMS
S y n t h e s i s , 221 (1978)
Ph CBF4 3
v
CH2C1
T e t r L e t t , 2771 (1978)
l
H
2
3
SECTION 331
:
ALCOHOL
-
381
NITRILE
1 ) H2NOCH2CH2NMe2
s
R-C----C-R'
2 ) NaBH4
3) H2C=0, H30e
El
' R-C----FH-R OH
*
Synthesis , 466 (1 977) Section 331
Alcohol
-
Nitrile
1 ) PhS02C=N+0 2) Na/Hg
b
JACS 101, 1319 (1979)
1 ) Me3SiCN
HO CN
*
A
1
I
Tetr Lett, 3773 (1978)
~80%
382
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 332
Alcohol
-
SECTION 332
Olefin
A l l y l i c and b e n z y l i c h y d r o x y l a t i o n (C=C-CH
+
C=C-C-OH,
etc.) i s
l i s t e d i n S e c t i o n 41 ( A l c o h o l s and Phenols from Hydrides).
L NaBH4
CeCl
Hp,
PhCH=CHCHO
6
100%
co
PhCH=CHCH20H
RhCl
BcS Japan 50, 2148 (1977)
83%
SECTION 332
ALCOHOL
-
OLEFIN
38 3
26, 995 (1977) B u l l Akad USSR Chem -
0
HO
T e t r L e t t , 2369 (1977)
O O H UTMS 1 ) 02’ hv
+
2 ) NaBH4
3 ) Bu4NF, MeCN
JACS 101, 4420 (1979)
54%
384
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
1) Me3SiOTf
SECTION 332
*
2 ) DBU
87% O O T M S
JACS 101 , 2738 (1979)
a
S y n t h e s i s , 62 (1979)
'gH1 3
1) C B O T f
2)
H20
+
*
' 6 " l M
OH
96%
Chem Lett, 1215 (1977) Et2A1TMP
99%
benzene
B u l l Chem SOC Japan 52, 1705 (1979)
SECTION 332
- OLEFIN
ALCOHOL
385
60%
JACS 99, 7067 (1977)
T e t r L e t t , 4093 (1978)
1) BuLi
CH2=CHSePh
2 ) PhCHO
,
HO
H
Bu/c=c\H
)HPh 71%
3 ) 03, ( i-Pr)+4H
ooH
JOC p3, 4252 (1978)
0
1 ) PhSeOH w
2) Me3COOH
-
JOC 43, 1689 (1978)
83%
386
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 332
S y n t h e s i s , 215 (1978)
+
-
85%
OH
6CHO JCS P e r k i n I , 2353 (1977)
1 ) Me3A1 -C1 2ZrCp2 2 ) BuLi C5H1 -C:CH 3 ) (CH20),
*
C H 5\11
/
Me/c=c\cH
T e t r L e t t , 2357 (1978)
H
82% 2 OH
SECTION 332
ALCOHOL
SeMe C7H13CH2-{H SeMe
1 ) BuLi
-
OLEFIN
387
SeMe C
I
2 ) CH20
C7H, 3CH= CH - CH20H
65%
T e t r L e t t , 1145 (1978)
78%
T e t r L e t t , 4089 (1978)
1 ) V O ( a ~ a c ) ~t-BuOOH , 2 ) MsCl, E t 3 N
~30% 3 ) Na(Ca),
B u l l Chem SOC Japan 52, 1757 (1979)
388
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 332
1 ) CuBr( Me$)
n -P rMgB r -
2 ) BuC-CH
*
3) LiC-CPr, HMPA
5) NH4C1 , H20 T e t r L e t t , 2465 (1978) 1
~
T
M
S
B U, ~ N F
BU-CHO
*
2 ) HC1, MeOH
OH I BU- CH 92% I CH2CH=CH2
T e t r L e t t , 3043 (1978)
1 ) Me3CCH0
Me3C
Me
70%ee Angew I n t Ed 17, 768 (1978)
Review : "Simp1 e Enol S " Chem Rev
79, 515
(1979)
SECTION 335
Also v i a :
ALDEHYDE
Acetylenes
Section 333
Aldehyde
-
- AMINE
389
Alcohols (Section 302)
-
Aldehvde
I(0W3
~~70%
JCS Perkin I, 1483 (1978) Section 334
Aldehyde
-
Amide
No a d d i t i o n a l examples
Section 335
H
Aldehyde
- Amine
1)
Q s
2) NaOMe
JACS 100, 7600 (1978)
54%
390
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Me I
aNH
SECTION 336
:
0
c1
B C g C H 2NC CH2Cl
S y n t h e s i s , 99 (1979)
18, 933 (1979) Angew I n t Ed -
S e c t i o n 336
Aldehyde
No a d d i t i o n a l examples
-
Ester
72%
ALDEHYDE
SECTION 337 Section 337
6
Aldehyde
-
-
ETHER, EPOXIDE
39 1
Ether, Epoxide
6
1 ) H2C=CH-CH2Br
K I , DMF
OCH2CH0
*
2) Os04, NaI04
72%
H20/ether
Synthesis, 202 (1979)
16, 789 (1977) Angew I n t Ed -
HO
py r id ine
70%
0 CHO
JOC 42, 813 (1977)
392
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 338
-
Aldehyde
SECTION 339
Halide
88%
T e t r L e t t , 2817 (1979)
6
1 ) LiC1C=CF2
Synthesis, 458 (1978)
t-BuOC1 76%
w
EtOH
EtO
EtO JOC 42, 1057 (1977)
S e c t i o n 339
Aldehyde
0
II Ph-C-CH2Br
-
Ketone
Et2NOH ____)
-
0 II Ph-C-CHO
JOC 42, 754 (1977)
78%
ALDEHYDE
SECTION 339
0s iMe
-t-Bu
-
KETONE
393
il
1 ) TiC14
Me2CH-CCH2CH2CH0
t
.O
80%
2) 5 0
Me2 CH-!-C1
JOC 43, 2551 (1978) C-HX 1 ) Br-CH2-CH(OEt)2
R
*
8
2 ) HOAc
R = a l k y l , Ph
35, 1745 (1 979) Tetrahedron -
JOC
42,
~60%
R-C-CH2CH2CH0
1819 (1977)
394
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 340
JCS Chem Comm, 100 (1979)
n VS Me
n-BuLi 1) -
, THF
2) C1CH2CH2CH(OEt)2
3)
t P
*
S
Me*CHO
Synth Corn 9, 147 (1979) Section 340
Aldehyde
-
Nitrile
I n d i a n J Chem 18B, 175 (1979)
SECTION 341
ALDEHYDE
8 Li CHCN
+
-
395
OLEFIN
1 ) THF
Q c
Me2C-CH2CH0
Me2C=CHCH0
OMe
80%
HCN
OMe
JCS Chem Corn, 779 (1979)
-
i-Pr,
Me
\
Me/c=c\
MgCl2
/H N-i
A-
-Pr
t
CH2=CHCN
MeOH
N
'd
H/
CH CH CN
\/
/ \
Me
65% Me
JCS Chem Comm, 565 (1977)
Section 341
Aldehyde
-
Olefin
For the o x i d a t i o n o f a l l y l i c alcohols t o o l e f i n i c aldehydes see a l s o Section 48 (Aldehydes from Alcohols).
396
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
6
SECTION 341
0
II
1 ) Me
48%
2 ) HC02H
JACS
99, 5453
Bu-CHO
(1977)
Bu
/--=\ICHO
2) MeOH, TsOH
60%
3 ) AcOH, H20
S y n t h e s i s , 132 (1979)
1 ) NBS, A I B N cc1 Bu-CH2CH2CH0
2) NaOH/H20
*
Bu
\ CHO w
MeOH, Bu4NHS04
S y n t h e s i s , 507 (1979)
86%
SECTION 341
Ph
-
ALDEHYDE
*
CH~OH
QLF 0 b
OLEFIN
397
OTs
Me
Ph*CHO
*
DMSO
85%
Chem L e t t , 369 (1978)
0; POCl
85% Et3N
ocH
T e t r L e t t , 2027 (1977)
0 I1 1 ) Ph-S-CH2C1 , L-BuOK
*
A
85%
T e t r L e t t , 1377 (1977)
CH3-( CH2)7-CH0
~40% Angew I n t Ed 18. 687 (1979)
398
COMPENDIUM
8
OF ORGANIC SYNTHETIC METHODS
1 ) Ph3P=CHOMe 1 2 ) 02, benzene
VOL 4
*
3) Ph3P, benzene
Synthesis, 67 (1978)
1) P h 3 P w O M e
*
2 ) H30@
T e t r L e t t , 3875 (1977)
JOC 43, 3788 (1978)
SECTION 341
60%
SECTION 341
-
ALDEHYDE
OLEFIN
399
dHO 97%
JACS
o
99, 7365
OE t
1 ) -Li
*
r
(1977)
0
8
/ 7
CHO %
2) H20, NaHC03
T e t r L e t t , 717 (1978) R N ,SnBu3 2 \ / H/c=c\H
CHCHO
BuLi
*
2) H3@
T e t r L e t t , 3589 (1977)
50%
400
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1 ) TiC14, Pr-CH=C
/TMS
\
Pr
SECTION 341
CH2C12
CH30CHC1
C,HO
*
Pr-CH=C
2) H p
\P r
79%
S y n t h e s i s , 721 (1977)
1 . C12CHOMe, T i C 1 4
*
PrCH=C ( P r ) TMS
79% PrCH=C( Pr)CHO
2. H20
Chem L e t t , 8 5 9 ( 1 9 7 8 )
Me-CH= C-OTMS
PhCH ( OEt ) JACS
99, 5827
(1977)
SECTION 341
ALDEHYDE
-
OLEFIN
401
1) LDA, -78O
PhSxCH20CH3
PhS
2) 5-C6Hl3Br
2 HgC12 HC1 -CH3CN
76% 0 Chem L e t t , 345 (1977)
14 Me-C-CH=CHS-4-Bu
n-BuLi
-n-Bu$=CHCHO
T e t r L e t t , 2809 (1979)
1) LDA, a l l y 1 Br 2) MeOS02F 3)
NaBH4
4 ) AgN03 T e t r L e t t , 5 and 9 (1978)
A1 so v i a : 8-Hydroxyal dehydes (Section 324)
89 %
402
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 342
Amide
-
SECTION 342
Amide
H Several additional examples. Chem Ber 112, 727 (1979)
Mn O2 NHNHC02Et
NHC02Et Tetr Lett, 4185 (1979)
Also via:
Dicarboxylic acids (Section 312) Diamines (Section 350)
SECTION 344
Section 343
AMIDE
Amide
-
-
403
ESTER
Amine
2 ) PhCOCl H2N(CH2)8NH2
*
8
H2N(CH2)8NHCPh
3) TFA I s r a e l J Chem 17, 248 (1979)
S e c t i o n 344
Amide
-
Ester
Synthesis, 704 (1977)
81%
404
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 344
H
SeCO, O2
72% Me
Me
Angew I n t Ed
8
~ C H 2 0 C ( ~ II 0H 2 ) a C c1 )i PhNH2
*
3,692
(1979)
1 4 8
MeOC(CH2)8CNHPh
98%
2) c l e a v e , e s t e r i f y
Can J Chem 0
56,
1562 (1978)
0
II
Ph-CFe( C O ) 4 t
c1 I P h - C= NP h
___L
2) E t O H
Ph 0 \ II Ph-CH-N-C-Ph I
COOEt
JACS 101, 4245 (1979)
61 %
AMIDE
SECTION 345
MeOfHC02Me Me2C=CH2
+
NHCOPh
-
405
EPOXIDE
-
NHCOPh I
CH- C02Me
NSA
I
Me2C=CH
52%
benzene
(NSA = naphthalenesulfonic a c i d )
-
Tetrahedron 33, 1533 (1977)
,NHAc PhCH=C
H2
\ COOMe
*
N H A c,* PhCH -CH
c h i r a l Rh c a t a l y s t s
~100%
\COOMe 55-96%ee
JACS 99, 5946 (1977)
T e t r L e t t , 1119 (1978) T e t r L e t t , 1635 (1978) Chem L e t t , 39 (1979)
Related methods:
Section 315 ( A c i d - h i d e ) Section 316 (Acid-Amine) Section 351 ( M i n e - E s t e r )
Section 345
Amide
-
No a d d i t i o n a l examples
Epoxide
406
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 346
Amide
-
SECTION 346
Halide 0
II
EtO-C-NHCl chromous c h l o r i d e *
AcO
&79% NHCOOEt
Can J Chem
55, 700
Can J Chem
56,
Chromous c h l o r i d e MeOH
(1977)
119 (1978)
*
92% 0 C‘ H 3
JOC 43, 3750 (1978)
SECTION 349
S e c t i o n 347
- OLEFIN
AMIDE
Amide
-
407
Ketone
No a d d i t i o n a l examples
S e c t i o n 348
Amide
-
Nitrile
No a d d i t i o n a l examples
S e c t i o n 349
Amide
-
8C-NMe2
Olefin
0
It
1 ) C0Cl2
*
JACS
6
101,4381
(1979)
\
4
CHCONMe2
/OLi 1 ) Me2SiCH=C
NMe,
43, 1947 (1978) JOC -
92%
408
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 350
Angew I n t Ed 18, 533 (1979)
T e t r L e t t , 2289 (1977)
A l s o v i a : O l e f i n i c a c i d s ( S e c t i o n 322)
S e c t i o n 350
Amine
-
Atnine
2 PhNH2 HgO*2HB F4
f PhiNt‘
S y n t h e s i s , 962 (1979)
NHPh
89%
SECTION 350
AMINE
-
-
409
AMINE
1 ) PdC12(PhCN)2
2 ) Me2NH
C8H1 7-CH=CH2
3 ) MCPBA
C8H1 7-;HNMe2 CH2NMe2
81 %
4) KBHa
T e t r L e t t , 163 (1978)
Me2CHBr
Me2CHNH
H2NH CHMe2
EtOH
J P r a k t Chem 321, 680 (1979)
Chem Ber 110, 1259 (1977)
80%
410
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 351
Amine
- Ester
R
BzBr, CH2C12
I Z-NH-CH-COOH
s
Z-NH-CH-COOH
SECTION 351
R4NC1, NaHC03 + -.
R
O
R I
O II
I II Z-NH-CH-C-OBZ
*
EtBr
Z-NH-CH-C-OEt
NaHC03, DMF
Synthesis, 957 and 961 (1979)
@P
H 3~- CH - coo0
TsOH, EtOH reflux
Qfjk OMe
s:!
TsOO H,N-CH-COOEt
-
Bull Chem SOC Japan 52, 1879 (1979) 1) LiNH(t-Bu) 2) H?
MeOH
* T
COOMe 47%
OMe
42, 2653 (1 977) JOC -
NH( t-Bu)
SECTION 352
AMINE
-
41 1
ETHER
- xNH2 1 ) BzBr
2) H30@
Me02C
80-90%
e> Me
93%ee
Angew I n t Ed 18, 863 (1979)
oxalic acid
68%
Me
T e t r L e t t , 809 (1979) Related methods:
Se c ti o n 315 (Acid-Amide) Se c ti o n 316 (Acid-Amine) Se c ti o n 344 ( Amide-Ester)
S e ct ion 352
Amine
-
No a d d i t i o n a l examples
Ether
412
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
S e c t i o n 353
Amine
-
Halide HF
H
Ph-CHF-CMe2 I NH2
____)
/N\ Ph-CH-
SECTION 354
CMe2
6
S e c t i o n 354
6
%80%
T e t r L e t t , 3247 (1978)
B ro
CH3CN
80%
Synth Corn 8, 549 (1978)
Amine
6
-
wNM
Ketone
e
Me2N=CH2 CF3C$
90%
L-
-
Tetrahedron 35, 613 (1979)
( H2C= CH - CH2
+N H
t
Zn ( OAc ) 4
Cd(OAc)2
0
* (1
II
C=CH-CH2-)2N-CH2-C-CH3
HC5C-CH20H T e t r L e t t , 3523 (1979)
45%
SECTION 356
S e c t i o n 355
AMINE
Amine
-
-
OLEFIN
41 3
Nitrile
H TH F
T e t r L e t t , 4663 (1979)
S e c t i o n 356
Amine
-
Olefin
S y n t h e s i s , 830 (1979) Li
1 ) Ph2POLH-NT\0 Ph-CHO
n
I PhCH=CH-NuO 2 ) NH4C1 3 ) KH T e t r L e t t , 2433 (1979)
99%
414
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 356
1) LDA CN I Ph-CH-NPh Ie M
2) 3) KOH
CH C1 2
H
*
Me I
\
/NPh
N C = ' \ p h
Synthesis, 127 (1979)
J Het Chem 14, 1419 (1977)
JOC 43, 3898 (1978)
72%
SECTION 357
ESTER
&--
- ESTER
41 5
TMS I L i CHCONMe2
40%
T e t r L e t t , 709 (1978)
S e c t i o n 357
Ester
-
Ester
B r - ( CH2) 5CH ( C02Me)2
2'3
100%
MeONa
JCS Chem Comm, 522 (1979) CH ( COOMe )
NaCH( COOMe)2 (Me2NI3P
THF o r DMSO
JACS 180, 3416 (1978)
55%
416
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
c1G
C
SECTION 357
l
Me02C%02Me
COOMe
*
COOMe 66%
phx
JCS Chem Cornm, 641 (1978)
/OMe PhCH=C O ‘ TMS
tl
C1HgCH2CCH3
+
fl C1 -C-OEt
1 ) TiC14, CH2C12
COOMe
*
2 ) H20
73%
Ph
T e t r L e t t , 2009 (1977)
HMPA
T e t r L e t t , 3737 (1978)
Also v i a :
D i c a r b o x y l i c a c i d s ( S e c t i o n 312) Hydroxyesters ( S e c t i o n 327) D i o l s ( S e c t i o n 323)
COOMe
ESTER - HALIDE
SECTION 359
Section 358
Ester
-
41 7
Ether, Epoxide 1 ) LiCH2COOEt
fi AMe Ph
43%
2) 2 LDA
Ph Me% Y O O E t
D
3) 12 T e t r L e t t , 4575 (1977)
COOEt CF3S02C1
CH( C O O E t ) 2
COOEt
100%
D
DBU
CH20H
T e t r L e t t , 3645 (1979)
Section 359
Ester
-
Halide
ccy"'
45%
JCS P e r k i n I , 2231 (1977)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
418
12, AcOH
SECTION 359
*
99%
Cu ( O A C ) ~ S y n t h e s i s , 402 (1978)
0
a..cl ,OAC
71 %
CH2C1
T e t r L e t t , 3523 (1977)
i
CH3-C-CI
L
C
H
O
*
ACO - CH - c i
97%
ZnCl H e l v Chim Acta 61 , 2047, 2059, 2165, 2381 (1978) S y n t h e s i s , 593 (1978)
SECTION 359
ESTER
-
HALIDE
1 ) LDA
H O
I II
Me C- C- OMe
41 9
Br 0 \
II
Me2C-C-OMe
P
79%
2 ) C B r 4 , THF JOC 43, 3687 (1978)
C8H17
Ru(I1) complex 1 -Decene
t
C C I ,COOH 3
*
+Il
85%
0
Chem L e t t , 363 (1978)
1 ) Me3SiCl, p y r idine
F OH
Ph- H-CH2COOEt
Q
*
2 ) PhPF4
Ph-CH-CH2COOEt I
92%
F
T e t r L e t t , 4507 (1978) TMS
I
C1 -C-C02t--Bu
I Li
44%
T e t r L e t t , 515 (1978)
420
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3
SECTION 360
1 ) BuLi 2) C l C O O E t
8
C13C-P(OEt)2
*
@COOEt
71 %
Synthesis, 31 (1978)
Review : "Synthesis and Synthetic U t i 1it y o f Hal o l actones"
Chem SOC Rev 8, 171 (1979)
Also v i a :
Haloacids (Section 319) Halohydrins (Section 329)
Section 360
t
Ester
CzC-OMe
-
Ketone
KC1O3 Os04, H20
b
hoM
JOC 43, 4245 (1978)
80%
SECTION 360
ESTER
-
KETONE
421
Chem L e t t , 369 (1978)
NHAc
R
1) t-BuOC1
'C /H-LH-COOMe 2) MeOH, NaOMe
R' R,R'
R i 'CH-CCOOMe
*
R
= H, a l k y l
Chem Ber 111 , 31 36 (1978)
Li I
(Me0 ) 2C-COOMe Ph-CH2-Br
TH F
COOMe I Ph-CH2-C(OMe)2
b
Synthesis
, 33
(1 979)
70%
422
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 360
1 ) LDA, THF/HMPA SEt Me0
2)
BzBr
3 ) TTN, MeOH
Ph
T e t r L e t t , 4115 ( 1 9 7 8 )
/ SMe
1) NaH, CH2
P hCH2CH2CN
'SOMe*
88
PhCH2CH2C-C-OEt
2 ) CuC12, EtOH
T e t r L e t t , 375 ( 1 9 7 8 )
18, 632 ( 1 9 7 9 ) Angew I n t Ed -
%60%
SECTION 360
ESTER
-
KETONE
423
8
fi
CH3( CH2)6C-C1
90%
CH3( CH2)6CCH2COOMe 2 ) MeOH
43, 2087 (1978) JOC -
1 ) BuLi
*
HOOC-CH2COOE t
0 II Me2CHCH2CCH2COOEt
98%
2 ) Me2CHCH2COC1
JOC 44, 310 (1979)
-
95%
Me I
Et4NF
V
O
E
Me
J C S Chem Comm, 64 (1977)
t
424
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
1) Ph3P=CHCOOMe 0 II C5H1 1C-C1
2) A
*
SECTION 360
0
II
C5H1 CCH2C02Me
%60%
3) C N H
L i e b i g s A n n , 282 (1977)
COOEt
70%
Synth Corn
g,
59 (1978)
Synthesis, 142 (1978)
SECTION 360
ESTER
WH
8
CH2=CHCMe
0
COOMe
fie -
KETONE
425
q u i n i n e - a c r y l o n i tri 1e polymer
0
98%
30%ee JACS 100, 7071 (1978)
DME
6
T e t r L e t t , 1193 (1979)
OCOPh
1 ) Pb(OCOPh)4 b
2 ) EtqNF
66%
OCOPh
JOC 42, 1051 (1977)
COOE t ethyl diazo(1ithio)acetate
JCS Perkin I , 1822 (1977)
426
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 360
8
1) LiCH2-C-O-t-Bu -
*
U
H2°
C-O-t-BU -
73%
T e t r L e t t , 4323 (1978)
e l e c t r o r e d u c t i on
COOE t
* Ac20, MeCN, Et4NOTs JACS
01o//,,
COOEt
99, 7396
COOEt
74%
(1977)
a,A COOEt
1)
~
2 ) NH4C1, H20
T e t r L e t t , 4597 (1978)
65%
SECTION 360
ESTER
-
KETONE
Synth Corn
C02Me
-
8,
42 7
53 (1978)
1 ) LDA, THF
&
2)
Br
JOC 43, 4650 (1978)
Me0
OMe
-
TMS 0
0-TMS COOMe
92%
JOC 42, 4166 (1977)
Mesz;
428
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
n
S
HgC12
_____)
6-
-
1 9 A
BuCCH2CH2COEt
EtOH/H20
U
84%
8, 279 (1978) Synth Comm __c
N‘ /
H38
T1 (OAc)3
___)
T e t r L e t t , 23 (1977)
Also v i a :
SECTION 360
Ketoacids (Section 320) Hydroxyketones (Section 330)
-80%
S E C T I O N 361
ESTER
Section 361
Ester
d
-
-
429
NITRILE
6 FOO Et
Nitrile
CH2CN
~HCN
1) LDA
*
2 ) ClCOOEt
86%
42, 2009 (1977) JOC EtOOC-CH2-CN
-
FN
CuO, 85”
t
CH3-(CH2)9-CH
75%
IOOEt
CH3- ( CH2)7-CH=CH2
Synthesis, 454 (1977) XOOEt
t
OMe
’
H\C;C/CooEt C7 C‘ N
-Q A1 C1
OMe
Chem B e r 110, 86 (1977)
62%
430
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
Ph3P= CH CN
+
SECTION 362
NC-CH=C(COOEt)2
O=C (COOE t ) 2 Synthesis, 626 (1977)
Section 362
Ester
-
Olefin
This s e c t i o n contains syntheses o f enol e s t e r s and e s t e r s o f unsaturated acids.
3 ) P0Cl3, E t 3 N T e t r L e t t , 2693 (1978)
Chem L e t t , 1039 (1979)
88%
SECTION 362
ESTER
-
OLEFIN
431
CHCOOEt
00
S-CH-COOEt
60%
Chem L e t t , 471 (1977)
6
1 ) Ph3P=CHOMe 2)
1
-6 COOMe
02, benzene
3 ) CH3COC1, p y r i d i n e
n
S y n t h e s i s , 67 (1 978)
GHO OACH2%
60%
( OE t )
L i OCHMe2
*
66%
TH F/ benzene
JOC 44, 4010 (1979) JOC 44, 4011 (1979)
+ i-Pr-CHO
-
i-Pr-CH=CHCOOEt
Tetrahedron 34, 997 (1978)
~~70%
432
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 362
2 ) @OH,
H202
[Pr3BMe]Cu
t
H
Pr
\
80%
/H
H /c=C\CooEt
T e t r L e t t , 3369 (1977)
cr
A1 C1
JACS 101, 5283 (1979)
1) Me3A1-C12ZrCp2 C5H1 -CECH
*
‘5v
H,
86 %
Me/ C=C\COOEt
2) ClCOOEt
T e t r L e t t , 2357 (1978)
( CH2=CHCH2) 2CuLi t
BU-CZC-COOEt
-
CH2=CH-CH2
T e t r L e t t , 1811 (1979)
COOEt 90%
SECTION 362
ESTER
BuCu-BEt3 Ph-C?C-CO2Et
- OLEFIN
*
433
Ph
\
/c=c\H Bu
96%
JOC 44, 1744 (1979)
[Bu3BMe] Cu t
DME
HC-C-COOEt
Bu
’
H
\c=c’ H
61% ‘COOEt
BCS Japan 50, 3431 (1977)
- 7cH 1) LDA
57%
y C H S C O N M e 2
2) MeSSMe
3) H20, H!3C12
T e t r L e t t , 2895 (1978)
91%
T e t r L e t t , 619 (1979)
434
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
,CH3 CH2=C \-Cl
SECTION 362
95%
+
0
3 A molecular seives
b'
G+
COOE t
JOC 1
42,3965
CF3S03CH2COOEt
*
2) DBU
(1977)
E , o o c ~ 89% /
/
(64:36 E:Z) T e t r L e t t , 1241 (1977)
1 ) MCPBA, Ac20, H2S04
0
2) Pd/C 3) KOH 4) HC1 Indian J CHem 15B, 214 (1977)
ESTER
SECTION 362
-
435
OLEFIN
1 ) LDA, THF/HMPA
\
MeO-
FOOMe
COOMe 2) a l l y l - I
Synth
Corn 7, 189 (1977)
CO, PdC12(PPh3)2
I
CMeEt I OH
&Me
7
THF, K2C03
T e t r L e t t , 133 (1979)
T e t r L e t t , 5167 (1978)
Et
85%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
436
&
COOEt
SECTION 362
OhcM
/cl Me C 2 \
N02
50%
Chem Lett, 189 (1977)
Chem Lett, 653 (1978)
% Br
N i (C0)4/KOAc
*
MeOH
Chem Lett, 773 (1978)
Review:
"Recent Methods for the Synthesis o f Conjugated Lactones"
-
Aldrichimica Acta 10, 64 (1977)
SECTION 362
ESTER
- OLEFIN
437
4
68%
C02Me
JACS
101,6429
(1979)
1) NaSePh
2 ) CH2N2 3) -PhSeH
toM 68%
\
T e t r L e t t , 4361 and 4369 (1977)
1 ) HOAc '6"13HH*TMs
2) BF3*Et20
*
'gH13
/==/
JACS 99, 1993 (1977)
81% OAc
438
COMPENDIUM
OF ORGANIC SYNTHETIC MEHTODS VOL 4
SECTION 362
“‘“M MeoTcoo 1 ) C13CCHO*H20, H2S04
a30%
2 ) Zn, HOAc
OMe
Q
3) EtOH, HC1
dMe
8
I n d i a n J Chem 15B, 103 (1977)
-
C02Et
1 ) LiTMP
2 ) C1C02Et JOC
6‘,
43,
2073 (1978)
Ac20
( CH3)2CHCH0
( CH3)2C=C
Et3N
Synth Comm
9,
PAC 69%
‘H
157 (1979)
CuC12, NaOAc HOAc
76%
Me
Angew I n t Ed 18, 866 (1979)
SECTION 364
Also v i a :
ETHER
-
HALIDE
439
Ace ty l e n i c e s t e r s (Section 306) O l e f i n i c a c i d s (Se c ti o n 322) B-Hydroxyesters (Section 327)
S e c t ion 363
Ether
-
Ether
See Sect ion 60A ( P r o t e c t i o n o f Aldehydes) and Section l8OA ( P r o t e c t i o n o f Ketones) f o r r e a c t i o n s i n v o l v i n g t h e f o r m a t i o n o f a c e t a l s and k e t a l s .
Q
CH( O E t \
I
OE t
CH-
CH
OMe
OMe
I
,.
OMe
Section 364
OE t
I
BCS Japan 51, 2059 (1978)
Ether
-
Halide
12, BzOH Cu ( OAc) *, AcOH
Synthesis, 402 (1978)
90%
440
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 365
I*, PhOH 70%
S y n t h e s i s , 67 (1979)
C12, hv CC14
Chem and I n d , 127 (1977)
S e c t i o n 365
E t h e r , Epoxide
-
Ketone
1 ) BuMgBr MeOCH2CN
*
8
MeOCH2C-Bu
82%
T e t r L e t t , 23 (1977)
-& A1 C1 3-NaC1
JOC
44,
3724 (1979)
99%
SECTION 367
ETHER
-
441
OLEFIN
1 ) EtMgBr 'gH1 3
'gH1 3
76%
13, 1062 (1977) JOC (USSR) -
1) MCPBA
*
dg""
0
JOC 42, 2077 (1977)
Section 366
Ether, Epoxide
-
Nitrile
No a d d i t i o n a l examples
Section 367
Ether
- Olefin
Related methods: P r o t e c t i o n o f Ketones (Section 180A).
86%
442
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 367
JOC 43, 3861 (1978) M e 3 S i C 1 , BuS03K Et N/ cy c 1oh e xsane
- 6
Synthesis, 34 (1979)
Li
JACS 101, 2225 (1979)
72%
SECTION 367
-
ETHER
0 NNHTs
1 ) BuLi
, TMEDA
2) Me3SiC1
OLEFIN
443
*
61 %
T e t r L e t t , 159 (1977)
Et
A1 C 13/ Et 3 N
( OE t )
'CH-CH
Bu /
Bu
ether
80%
CHOEt
H e l v Chim Acta 62, 1451 (1979)
Synth Comrn 7, 327 (1977)
Me2N0
BU -CH= C
/H
\09p
-
A
C Cl0
Bu H
S y n t h e s i s , 504 (1979)
81%
444
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 367
b
93%
-
BZ - 0- CH - COOH
H OBz
PhS02C1
&OH
pyr i d i ne
Synthesis, 388 (1979)
1 1 ) Ph2P-CH20Me 2 ) NaH, THF
6 HCOMe
*
57%
JCS Chem Corn, 314 (1977)
0
I1
Ph,P-;H-Li
OMe
+
Me
Ph
2 ) NaH
Me0 \C/H
II
Me
JCS Perkin I , 3099 (1979) 1 ) Ph3P 2 ) PhCOONa
+
3) t-AmONO
Tetr Lett, 2149 (1979)
89%
SECTION 367
ETHER
@ G
CH2PPh3Br a
O
H
-
OLEFIN
445
n-PrCOC1 Et3N
T e t r L e t t , 2145 (1979)
BY@
0
0
Ph
75% (n=3)
Ph3P- ( CH2),-O-C-Ph 82 %
Ph
T e t r L e t t , 5 (1979)
T e t r L e t t , 2995 (1979)
(n=4)
446
COMPENDIUM
OF ORGANIC
SYNTHETIC
CH2=CHOAc H2S04 ClCH2CH20H
Hg ( OAc l2
*
METHODS VOL 4
SECTION
C1CH2CH20CH=CH2
368
a45L
JOC (USSR) 13, 606 (1977)
Section 368
Halide
-
Halide
Halocyclopropanations a r e found i n S e c t i o n 74 (A1 k y l s from O l e f i n s ) .
Ph-CHO
SOCl
DMF
-
c1 1
Ph-C-C1
li
JOC 43, 4367 (1978) L
JCS P e r k i n I
1354 (1979)
90%
HALIDE
SECTION 368
-
HALIDE
447
Et-CEC-Et
75% TH F
F F
JOC 44, 3872 (1979)
0
HC1, H202 phase-transfer c a t .
Synthesis , 676 ( 1 977)
XeF2 Ph-CH=CHCH3
Ph-CH-$H-CH3 I
60%
F F JOC 42, 1559 (1977)
Et Et4N@Clo,
F4
Et3N
a::::
Chem L e t t , 1013 (1977)
58%
448
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 369
Halide
-
Ketone
SECTION 369
0
Br2’ hv
100%
JCS Perkin I
14 Me-C-CH2Me ?I Me-C-CH-Me
1:
NBS
501 (1977)
0 II Me-C-CBr2Me
95%
8
NBS
95%
Me-C-CBr-Me
k1
JOC 42, 3527 (1977)
0 II Ph-C-CH2Ph
PhIC12
*
hv, benzene
JOC (USSR)
8
Ph-C-$HPh
c1
2,1414
(1978)
8 0%
SECTION 369
HALIDE
-
449
KETONE
65%
S y n t h e s i s , 140 (1978)
CH2NMe3 B r 3
*
0
Br-&l
78%
0
S y n t h e s i s , 64 (1979)
1)
0
(:)
, TiC14
H 3
2) B r 2 , CH2C12
0 II
93% CH2Br
Acta Chem Scand B32, 646 (1979)
450
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
8 Me- C- CH2 -C-Me I0I
SECTION 369
0 fi II Me-C-CC1 *-C-Me
CF3S02C1
~-*
100%
DBU T e t r L e t t , 3643 (1979)
JCS Chem Corn, 479 (1979)
T e t r L e t t , 725 (1979)
1) CF3CF20F
*
&F
85%
2 ) Zn, HOAc
JACS
101,2782
(1979)
12, TlOAc 3
HOAc
JCS P e r k i n I, 126 (1978)
46%
SECTION 369
HALIDE
-
KETONE
451
1) AgOAc, I2
84%
2 ) Et3NHF
JOC 44, 1731 (1979)
1 ) c1 3c'L'cc1 2) H3
8
3 ) NaHC03
3
-
bcl
JACS 99, 6672 (1977)
T e t r L e t t , 759 (1977)
T e t r L e t t , 2797 (1977)
65-90%
452
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
P
2 NCS
*
1 97%
CC14 Synth
SECTION 369
Corn 8, 75 (1978)
0
65%
JOC 42, 4268 (1977)
hv, 02 p y r i d i n e , FeC13 40%
Chem Lett , 161 (1978)
SECTION 369
HALIDE
-
KETONE
453
F’
1 ) Ph-S-CH3
(3
c1Q
*
94%
2) Et3N Chem L e t t , 995 (1977)
T e t r L e t t , 3653 (1979)
S y n t h e s i s , 139 (1978)
Me$
8
I
- C- CH2 B r
Br
AgBF4
0 II Me2C-C-CH2Br I F
T e t r L e t t , 3357 (1979)
87%
454
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
8
act. Zn , C13CCC1
*
P0Cl3
&Il
70% c1
JOC
V
SECTION 369
43,
2879 (1978)
CH2C1
85%
JOC 42 , 459 (1977)
0 II Ph-C-C1
pyridine/THF, ZnF2
*
0 II Ph-C-CF( CF3)2
( CF3)2CFZnI Also works w i t h anhydrides, Chem L e t t , 81 (1977)
(X=C1 , B r )
2)
A
T e t r L e t t , 1225 (1977) Chem L e t t , 209 (1979)
89 %
SECTION 369
HALIDE
6 0 II
0
c1
-
KETONE
455
1 ) LiC1C=CF2
0 II
2 ) MeLi
%30%
S y n t h e s i s , 458 ( 1 978)
0
I I I I1
t-BU-C-CH-P( O E t ) 2 c1
n-BuLi
*
t
76%
Ph-CHO S y n t h e s i s , 29 (1978)
HBr, hv
b C H 3 CH2CH2 CH2Br
93%
pentane
S y n t h e s i s o f s e v e r a l a d d i t i o n a l v i n y l ketones and t h e i r c o n v e r s i o n t o w-bromoketones a r e a l s o presented.
JOC 42, 1709 (1977)
456
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Section 370
Halide
+
-
Nitrile
-t-BUONO
SECTION 370
6 c1
CUCl
CH2=CHCN
i
CHCN
N02
JOC 4 2 , 2431 (1977)
Chem L e t t , 1117 (1979)
Review: "Preparation and Reactions o f Chloro-derivatives o f Nitriles"
Russ Chem Rev 48, 282 (1979)
93%
SECTION 371
Section 371
HALIDE
Halide
-
-
457
OLEFIN
Olefin
CuC12-LiC1 Ph-C=C-Et
Ph
*
he CN
\
/cl
94%
c1/c=c\
Et
Ph
\
/I c1/ c=C\Et
MeCN
100%
JCS P e r k i n I , 676 (1977) 1 ) [EtCuBrIMgBr Ph-CECH
Ph
\
*
=c, Et
2 ) NBS
/H
,c
>go% Br
Rec Trav Chim 96, 168 (1977)
1 ) Cp2ZrC12, Me3A1
Bu
2 ) 12, THF
/c=c\ Me
*
Bu-CZCH
\
Synthesis , 501 (1 979)
YH I
85%
458
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
C:CH
9
1 ) LiA1H4
2) acetone 3) IC1
SECTION 371
/I H/c=c\cl
~
89%
JACS 101, 5101 (1979)
Ph-CzC-Me
1 ) TeC14
2) 12, MeCN
Ph
*
c1
\ ,Me /c=c\I
85%
Chem Lett, 1357 (1979)
8 0
Ph-CZCH
Et3NH HC12
b
Ph
c1
\
/C=CH2
JCS Perkin I, 1797 (1977)
73%
HALIDE
SECTION 371
Bu
\
-
459
OLEFIN
/H
2-c\cu
Et
Et
*MgBr
Rec Trav
96, 168
-
NBS (X=Br) PMgBr
Pr
\
E t/c=c\H
o r NCS ( x = C l )
(1977)
Pr
\
Et
/x
%go%
/c=c\H
T e t r L e t t , 3545 (1977) 1 ) Br2 Bu-CH=CHSiMe
BuCH=CHBr
3
74%
2) alumina, pentane
Synth Comm
1 ) Br2
L-BuHTMS
7,475
(1977)
L-Bu 70%
H
H
2 ) KF, Me2S0 o r NaOMe, MeOH
H
o r A1203, Pentane
JOC 43, 4424 (1978)
H
460
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 371
m
'8"17
TMS
/='
I
1) I C 1 2) NaOMe
75%
'gH1 7
T e t r L e t t , 1073 (1979)
1) P h S e B r
C6H1 3-CH=CH2
2) 03
Br I
C6Hl 3-C=CH2
85%
3) i--Pr2NH
T e t r L e t t , 3909 (1977)
Q
CH= CH-CMe3
OMe
Q F I
0
II
1) CH3CNHBr, HF
2 ) KOH
-
C- CH CMe3
OMe
S y n t h e s i s , 217 (1978)
74%
SECTION 371
HALIDE
-
OLEFIN
461
(yl 0NCS
90%
PhSeSePh
Several o t h e r cases g i v e a l l y 1 i c c h l o r i d e s .
JOC 44, 4204 (1979)
Bu
6"
Bu
\
- CHo
\ C=CHC1 1
E t 3 N , Et4NC1
82%
Ph-40
Chem L e t t , 465 (1978)
( Me2N)3P=CC1 C5H1 CHO
6
*
C5H1 CH=CCl
94%
T e t r L e t t , 1239 (1977)
94%
JCS Chem Comm, 446 (1978)
462
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
CBr2F2- ( Me2N) 3P
n-C6H13CH0
*
SECTION 371
n-C6H1 3CH=CF2
80%
tr ig 1yme Chem L e t t , 983 (1979)
80
[Ph3P-C( CF3)2] i n s i t u Ph-CHO
*
PhCH=C( CF3)2
50%
T e t r L e t t , 3397 (1979)
8 Li
80%
1 ) PhS-!H-C1
*
CH3- ( CH2) 4-CH2Br
CH3 ( CH2)1 4-CH=CHC1
2) A , xylene
T e t r L e t t , 617 (1979)
11 HBr
fiTMS 85%
w
‘gH1 3
H
2) BF3*Et20
JACS 99, 1993 (1977)
Br
SECTION 371
HALIDE
-
463
OLEFIN
Br
JOC 4 2 , 418 (1977)
0 II c1 3c-c-cc1
CH20H
100%
Ph3P
JOC
CH2C1
44,
359 (1979)
PPh3
CH2=CH- CH-CH3 I OH
CH2=CH-CH-CH
c1 3c-c-cc1 II 0
T e t r L e t t , 2999 (1977) cc1
Ru ( II)complex Chem L e t t , 115 (1978)
I
3 94%
464
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
H2C=CH-CC1 2 L i
SECTION 371
Y
*
C1
39%
CH=CH2
S y n t h e s i s , 425 (1979)
S y n t h e s i s , 370 (1978)
fi
Me-C-O-CH2
\c=c/H
Ph'
\H2NEt2
8
C1 COOEt
'
Me-C-O-CH2 &
Ph/c=c\
Synthesis, 786 (1977)
91%
/H
CH2C1
SECTION 372
Section 372
KETONE
Ketone
0 OH II I Ph-C-CH-Ph
-
-
465
KETONE
Ketone
K3 Fe ( CN 16
95%
NaOH, MeOH
Chem and I n d , 741 (1977)
8
1 ) PhNHS02CF3 , K2C03
*
CH3CHBrC-C8H1 7
All CH3C-C-C8H1
92 %
2) HC1
-
JOC 44, 1835 (1979)
1 ) S0Cl2, P Y r 0 II Ph-C-CH2Ph
2 ) Morphol i n e
*
0 0
II II Ph-C-C-Ph
3 ) HC1/H20
T e t r L e t t , 695 (1977)
80%
466
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
-
SECTION 372
SMe
NaH, THF
T e t r L e t t , 5021 ( 1 9 7 8 )
1 ) TsOH,
C>NH2
2) NCS
Ph
ji,r
Ph
3 ) H30@
0
84%
4 ) NaOMe
JOC 43, 2933 ( 1 9 7 8 ) KMn04, H20 Ph-CEC-Pr
+
fii
Ph-C-C-Pr
CH2C1 2, Adogen
S y n t h e s i s , 462 ( 1 9 7 8 )
81 %
SECTION 372
KETONE
-
KETONE
467
acetone
JOC 44, 1574 (1979)
1 ) BuLi
H
’s‘
141
Et-C-C-Et
70%
3) E t I
JCS Chem Comm, 691 (1977)
1) BuLi TS- CH- N= C I Ph
8R
2 ) MeCOCl
Ph-C-C-Me
73%
3 ) H30@ T e t r L e t t , 4233 (1977)
1 ) NaH, THF/HMPT 2 ) Me1 53% 3 ) TTN, MeOH
T e t r L e t t , 4115 (1978)
468
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Ph
Me2CHI , Bu4NF CHCl
*
SECTION 372
pry 90%
JCS P e r k i n I, 1743 (1977)
I
Et4NF
b0
JCS Chem Comm, 64 (1977)
6;.
t-BuLi 1) -
, THF
*
2) Pentyl I o d i d e
‘gH1 1
91%
JOC 42, 3755 (1977)
1) 71 %
2) PhCOCl
T e t r L e t t , 1187 (1977)
SECTION 372
KETONE
-
KETONE
469
1 ) LDA 2) i-PrCOC1
FNMe2 n-Pr -
/\
Me
3 ) H3@,
*
60%
MeOH
T e t r L e t t , 2853 (1978)
0
"
0
II
-C-Pr
U
94%
3 ) H20 T e t r L e t t , 1339 (1979)
0
II
)-,
/\
Et
Et
1 ) LDA
0 Fi It BzCH C-CH-C-Et 2
2) H30@
1 CH3
+
q'' Cl
BZ
0
T e t r L e t t , 4095 (1979)
93%
470
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 372
RCOSeK
*
+
1 9 ;
R-C-CH2-C-R
'
%30-80%
2) L-CgH11OK BrCH2 COR ' R, R ' = s u b s t . Ph, a l k y l Chem L e t t , 1007 (1978)
Angew I n t Ed 17, 204 (1978)
JACS 99, 5222 (1977)
SECTION 372
KETONE
n
1) BuFi
sXs H R
2)
I
-
, THF/HMPT
I
KETONE
471
* %R
US %70-95%
T e t r L e t t , 3549 (1977) T e t r L e t t , 2695 (1979) 81 %
Can be used t o f o r m cyclopentenones JOC
42,
2545 (1977)
30, 1000 (1976) Acta Chem Scand ( B ) -
472
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
H C-C-COP h
SECTION 372
Chem Ber 112, 3221 (1979)
CH3CH0
0 9 +
thiazolium salts
*
% ? Y O 0M e 73%
&OMe
OMe
Chem Ber 1 1 1 , 2825 (1978) Chem Ber 112, 84 (1979)
ONYCH2 Li
1 ) THF, (COOH)2
t
2) Amberlite IR-120
vc=
Me
SMe
+
A
&
H
60%
I
II 0
CHPr
J Chem Research (S), 68 (1978)
SECTION 372
KETONE
-
KETONE
473
Tetr Lett, 3741 (1977)
Chem .Lett, 171 (1977)
al:d
Me
OH
q Q e
pyridine Pb(0Ac)4 4
0
0M
OTMS
e 70%
Chem Lett, 1433 (1978) Review: "Synthesis of Polyketide-type Aromatic Natural Products by Biogenetically Modeled Routes" Tetrahedron 33, 21 59 (1 977)
474
COMPENDIUM
Section 373
OF ORGANIC SYNTHETIC METHODS VOL 4
Ketone
-
SECTION 373
Nitrile
1 ) Et2NLi, THF
P
2) Pr-d-O-C02Et
*
E t - CH2CN
0 Pr-hY-CN I Et
74%
T e t r L e t t , 1585 (1979)
OH I Me2CCN, KCN
*
18-crown-6
0
benzene
T e t r L e t t , 1117 (1977)
2 ) CF3COOH
NC L i
3 ) NH40H
4) HC1
JOC
44,
CN
3275 (1979)
KETONE - OLEFIN
SECTION 374
9
47 5
PhSCH2CN
SPh 90%
LDA/THF
0
0
Tetr Lett, 1121 (1979)
fi E t- CHBr- C
MegSi CN
\
Br
_____)
0
II Et-CHBr-C-CN
64%
Me3Si C1
Synthesis, 204 (1979)
Section 374
Ketone - O l e f i t
For the oxidation of a l l y l i c alcohols t o o l e f i n i c ketones, see Section 168 (Ketones from Alcohols and Phenols). For t h e oxidation of a l l y l i c methylene groups (C=C-CH2 -+ C=C-CO), see Section 170, Vol. 1 and 2 (Ketones from Alkyls and Methylenes). For the alkylation of o l e f i n i c ketones, see a l s o Section 177, Vol. 1 and 2 (Ketones from Ketones) and Section 74 (Alkyls from O l e f i n s ) , Vols. 3 and 4 f o r conjugate alkylations.
476
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
I
SECTION 374
t-BuOH , PdCl
cholestane
80%
HC1, 80"
S y n t h e s i s , 773 (1977)
P I R
PhSe-0-Se-Ph 39-92% 0
JCS Chem Corn, 130 (1978)
Se02
C7H1 5-CH2-CH=CH2
0
II
C7H1 5-C-CH=CH2
61 %
t-BUOOH
JACS 9 9 , 5526 (1977)
1 ) PhLi 0
0
2 ) pyridinium * c h l orochromate
81 % 0QPh
JOC 4 2 , 682 (1977)
KETONE - OLEFIN
SECTION 374
477
benzene, HOAc w
Ph
Ph
Pd( O A C ) ~ JOC 43, 724 (1978)
1) Me2CuLi 2 ) Me3SiCl 3) Pd(OAcl2, O
e JOC 43, 1011 (1978)
1 ) MepS=CuBr
2 ) c-C6H1 3C-CH EtMgBr
L t 0 70% e6H13
4) NH4C1 JACS 99, 253 (1977)
T e t r L e t t , 3505 (1977)
478 COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 374
3) oxidation
Q
JCS Chem Corn, 821 (1978)
oA
1 ) Me-C-S-Ph A1
_____)
2) CaCO3, A
JOC 44, 450 (1979)
fl
1) (
NaH, THF
2) HCOOH
b
XO =
54%
8
-COOEt, Et -CN, -C-R JOC 43, 1817 (1978)
53-83%
SECTION 374
KETONE
-
OLEFIN
479
1 ) Me2NCH(OMe)2
* 51 %
2 ) BuLi
JOC 43, 4248 (1978)
1 ) PhLi 2 ) Me1 89%
1
3 ) H2Cr207 S02Ph
Me
4) DBU
JACS 100, 346 (1978)
Can J Chem
56,
2786 (1978)
480
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
Ph - C X H t
8
t-BuCO B e
Synthesis, 324 (1977)
JOC 42, 1581 (1977) OTMS
JOC 42, 3961 (1977)
SECTION 374
SECTION 374
KETONE
6
-
OLEFIN
48 1
DDQ, HMDS
68% benzene T e t r L e t t , 3455 (1978)
OSiMe3
1 ) 600"
2) H30@
'gH1 1 ( f r o m a1 kyl a t i o n o f norbornanone) T e t r L e t t , 3945 (1979)
3 ) MeOH Angew I n t Ed 16, 413 (1977)
T e t r L e t t , 4971 (1979)
80%
482
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 374
CH2TMS
I
8
CH2=C-CH=CH2
Me2CHCH2CC1
7 7%
T e t r L e t t , 429 (1979)
m
1) PCC 78% 2 ) TsOH
T e t r L e t t , 2461 (1978)
1 ) Mg, THF 2 ) CuBr(Me2S)
Br
AB-6)
62%
3)
@*
4) H C l , H20 T e t r L e t t , 4217 (1978)
SECTION 374
- OLEFIN
KETONE
483
EtO 0
0
JOC 43, 4673 (1978)
7;
TMS-0
2) TsOH, toluene
&77%
mol. seives, reflux
t
Ph
\
CHO
JOC 44, 462 (1979)
Na2C03, H20
benzene, R4NC1
55% Ph
Synthesis, 107 (1979)
484
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 374
S y n t h e s i s , 187 (1979)
HC1O4 HC02H
c1
0
B u l l Chem SOC Japan 52, 2978 (1979)
I-
C-C-Pr
'
t-BuCuLi
'.
t-BU
~87%
't-Bu
Synth Comm 9, 41 (1979)
KETONE
SECTION 374
-
OLEFIN
-
485
1 ) MeOS02F
87%
2 ) MeLi
3) T e t r L e t t , 5 (1978) "Me2
1 ) Me' 2)
'd'CH2Li
CUCl2
*
o=";o ~80%
T e t r L e t t , 13 (1978)
JOC 44, 105 (1979)
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
486
CH31, CO
Ph
/ -
“2 ( co 18
SECTION 374
Phw 86%
0
T e t r L e t t , 2 6 6 5 (1979)
CH3COC1
I ,
A1 C1
0 [CH3CH2CH$e( 4-
JOC 43, 710 (1978)
CO)4]
-
0
/O\
Ph-CH-CH2 Chem L e t t , 1067 (1979)
97% 0
-
KETONE
SECTION 374
SCONMe2
-
48 7
OLEFIN
1) LDA , MeSSMe
*
0
2) LDA, BuI 3) Hg0,BF3
9
59%
H20
T e t r L e t t , 2895 (1978)
0-0
, CF3COOo
e
H2NMePh
*
THF
T e t r L e t t , 2955 (1978)
1 ) BuLi
Bu
2) E t I
E
w Bu
t
OMe
0
T e t r L e t t , 1137 (1978) OMe
0
OMe
0 Synthesis, 521 (1979)
91 %
*-
488
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 374
4t
Ce / B ~ o ~
OH
hyd r oqu inone
-
0
Ce4y8ro3
96%
q u i none
Synth Corm 9, 237 (1979)
T e t r L e t t , 3753 (1978)
42%
T e t r L e t t , 3403 (1977)
57%
SECTION 375
NITRILE
-
NITRILE
489
ZnCl
+
CH2Cl
Br
18%
33%
Angew Int Ed 18, 163 (1979) 1 ) BuLi Ph2P
A
Ph
88%
2) CH3CCH3
3) NaH, THF JCS Chem Corn, 988 (1978)
NEt , CH2C12 JACS 99 6008 (1977) Section 375
Nitrile
No additional examples
-
Nitrile
73%
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
490
Section 376
Nitrile
-
Olefin KCN, PdL4
BU
b
Br
SECTION 376
Bu
CN
96%
crown e t h e r , benzene T e t r L e t t , 4429 (1977)
1) Ph-CEC-CN
Bu[CuBr]MgCl
8 2) H30
*
Ph >=CHCN
96%
Bu Synthesis, 454 (1978)
n-Bu-CX-CN
1) LiA1H4
H
\
-n -Bu Synthesis
[l C’=C’H ] C1 CN
‘CuBr
MgBr
TH F
Synthesis
/c=c\H
90%
430 (1 979)
Me
\ /H Bu/c=c\cN
784 (1977)
97%
SECTION 376
NITRILE
-
491
OLEFIN
CN
Me CN
Na2S
70%
Q
6
T e t r L e t t , 763 (1978)
KOH w -,
CH3CN
78%
Synthesis, 629 (1977)
KOH, CH3CN
Ph-CHO
PhCH=CHCN
82%
44, 4640 (1979) JOC ,CN
188
FHO
&
-
Ph2P CH-CN 7
TH F
N02 Synthesis, 126 (1977)
c90%
492
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
L
t
-
SECTION 376
B u L i , THF
-i-Pr-CH=CHCN
%70%
-i-Pr-CHO Tetrahedron
34,
997 (1978)
'8
S y n t h e s i s , 884 (1979) Me
ISII
EtO-C-S-CH-CN NaOH, H20/MeCN R,NC1
*
S y n t h e s i s , 8 9 0 (1979)
56%
SECTION 377
S e c t i o n 377
OLEFIN
Olefin
-
-
493
Olefin 1 ) MeLi
2) L i , NH3/EtOH
0
OLEFIN
*Y-Y I
1
98%
JOC 44, 1159 (1979) 1 ) NBS 75% 2) LiF, Li2C03
HMPT Synthesis, 279 (1977)
LiA1H4
74%
Et20
T e t r L e t t , 947 (1977)
L
CECH
1 ) Me3A1-C1 *ZrCp2
70%
2 ) BrCH=CH2, ZnC12, C1 2PdL2, D i BAH
\
JACS 100, 2256 (1978)
494
COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 377
C7H1 5 - C ~ C H
BSC France, 1173 (1976)
1) SiapBH
C1 (CH2)3CrCH
2) MeCu
70% JACS
Z r Cp C1
+ I
99,
5652 (1977)
- \ PdL4
‘gH1 1
Bu
Bu
T e t r L e t t , 1027 (1978)
Bu T e t r L e t t , 1137 (1979)
91%
SECTION 377
9
2
495
/H
H/c=c\
2
- OLEFIN
OLEFIN
HgCl
6
-8
JOC 42, 1680 (1977) T i C1 3/LiA1 H4
87%
-
JOC 43, 3249 (1978) Me2C=CHL i t
ether
Synthesis, 528 (1978)
1) CH2=C(OLi)2 Ph
Pr
2) MeO, H
+
O ,Me NMe
T e t r L e t t , 2953 (1978)
75%
496
COMPENDIUM
OF ORGANIC SYNTHETIC METHODS VOL 4
SECTION 377
tMe
6
1 ) Ph-S-Me, THF, II 0 Ph3CH, BuLi 2) A 1 / H g TH F/ H 20/ AcOH
*6
101 , 3 6 0 2 (1979) JACS -
1 ) L i , NH3/EtOH
80%
2 ) HC1, H20/MeOH/THF P T M S
JOC
44,
-
3784 (1979)
hv
Ph
Ph
87%
Ph
JACS 99, 2342 ( 1 9 7 7 )
SECTION 377
Review:
OLEFIN
- OLEFIN
497
"Synthesis o f Polyenes v i a Phosphonium Y1 i d e s " Pure and Appl Chem 51, 515 (1979)
Review:
"The Methods o f Synthesis and P r o p e r t i e s o f Conjugated
E n a l l e n i c Hydrocarbons"
-
Russ Chem Rev 47, 470 (1978)