Compendium of Organic Synthetic Methods Volume 3

Compendium of Organic Synthetic Methods Volume 3

LOUIS S. HEGEDUS and

LEROY WADE DEPARTMENT OF CHEMISTRY COLORADO STATE UNIVERSITY FORT COLLINS, COLORADO

A Wiley-lnterscience Publication JOHN WILEY & SONS, New York

Chichester

-

Brisbane

9

Toronto

A NOTE TO THE READER

This book has been electronically reproduced fiom digital information stored at John Wiley & Sons, Inc. We are pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.

Copyright @ 1977, by John Wiley & Sons, Inc. All rights reserved. Published simultaneously i n Canada. Reproduction or translation of any part of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley 8 Sons, Inc. Library of Congress Catalog Card Number: 71-162800

ISBN 0-471-36752-4 Printed i n the United States of America 20 19 18 17 16 15 14 13 12 1 1

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 reaction type rather than by the author’s name or publication date. We are honored by the opportunity to bring this useful work up to date. Compendium of Organic Synthetic Methods, Volume 3, presents the functional group transformations and difunctional compound preparations of 1974, 1975, and 1976. We have attempted t o follow as closely as possible the classification schemes of the first two 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 wellorganized, 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. Anyone who has ever typed a research paper with structures can understand what a Gargantuan project the preparation of the cameraready copy for this volume has been. Linda Benedict and Jackie Swinehart completed the entire project almost more quickly than our proofreaders, Gary Allen, Joel Slade and Robert Williams, could make corrections. The authors would like to express their thanks to these people for their dedicated work. Louis S. Hegedus Leroy Wade Fort Collins, Colorado June, 1977 iii

CONTENTS ABBREVIATIONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION

1 PREPARATION OF ACETYLENES 2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES

3 PREPARATION OF ALCOHOLS AND PHENOLS 4 PREPARATION OF ALDEHYDES 5 PREPARATION OF ALKYLS. METHYLENES, AND ARYLS 6 PREPARATION OF 7 PREPARATION OF 8 PREPARATION OF 9 PREPARATION OF 10 PREPARATION OF 1 1 PREPARATION OF

12 PREPARATION 13 PREPARATION 14 PREPARATION 15 PREPARATION

OF OF OF OF

AMIDES AMINES ESTERS ETHERS AND EPOXIDES HALIDES AND SULFONATES HYDRIDES KETONES NITRILES OLEFINS DlFUNCTIONAL COMPOUNDS

vii ix X

xi

1

8 24 66 88 134 149 178 204 218 235 248 296 305 336

ABBREVIATIONS The authors have attempted to use only abbreviations whose meaning will be readily apparent t o the reader. Some of those more commonly used are the following:

Ac Bu

Bz

CP DCC DDQ DIBAL DME DMF DMSO Et Hex HMPA, HMPT L LDA MCPBA Me Ms MVK NBS NCS Ni Oct Ph, 4 Pr PYr

acetyl butyl benzyl cyclopentadienyl d icyclohexylca rbod iim ide 2,3-dichloro-5,6-dicyanobenzoquinone diisobutylaluminum hydride 1,2-dirnethoxyethane dimethylforrnamide dimethyl sulfoxide ethyl hexyl hexarnethylphosphoramide (hexamethylphosphoric t r iam ide) triphenylphosphine ligand (if not specified) Iith ium d iisop ropy la m ide meta-chloroperbenzoic acid methyl methanesulfonyl methyl vinyl ketone N-brornosuccinirnide N-chforosuccinimide Raney nickel octyl phenyl ProPYI pyr idine vii

viii

Sia

Tf T FA T FAA THF THP TMS TS

A 6 6R EVIAT1ONS

secondary-isoamyl trifluoromethane sulfonate trifluoroacetic acid trifluoroacetic anhydride tetra hydrof u ran tetrqhydropyranyl trimethylsilyl p-toluenesulfonyl

-. x

5

8 4

1

1

7

Miscellaneous compounds 15

Olefins

Nitriles

6

Ketones 12

Hydrides (RH)

Halides. sulfonates, sulfates 10

Ethers, epoxides

Esters

Amines

Amides

Alkyls, rnethylenes, aryls

Aldehydes

Carboxylic acids, acid halides, anhydrides Alcohols, phenols

Acetylenes

Sections-heavy type Pages-light type

48 49

33

34

19

38

20 30 20

29

19

51 45 55

51 44

43

40

42

41

19

27

26

17

25

39

32

38

26

26

33 40 37

15

23

14

21

13

13

84

60

83

59

58 83

82

56

78

55

77 54 78

53

76

51

76

50

74

69

67

18

25

47

8

32

66

46

17

24

31

16

8

133

75

111

74

107

72

105

71

94

70

93

69

68 92

91

65

89 63 89 64 90

62

61

88

160

99

154

97

153

96

150

94

150

93

92

149

163

204

218

137

136

218

163

147

167

105

166

104

165

88 103

147

235

296

196

305

249

308

167 182 197

166

248

219

210

208

223

142 223

222

296

263

299

296

171 186

261

316

315

200

312

199

309

299

242

240

267

174

266

300

300

317

204

316

158 173 188 203

264

157 172 187 202

239

254

169 184

197

116

195

212

210

227

146

224

215

232

231

201

234

150

119 134 149

201

118

198

301

301

331

207 324

319

303

289

303

332

180 195 210

286

179 194 209

285

178 193

273

177

272

176 191

268

115 130 145 160 175 190 205~

194

114 129 144

190

113

189

111

188

109 124 139

186

108 123 138 153 168 183 198

178

107

106

178

87 102 117 132 147

146

86 101

161

85 100

146

139 82 143

81

138

79

138

78

135

77

76

134

INDEX, MONOFUNCTIONAL COMPOUNDS

Blanks in the table correspond to sections for which no additional examples were found in the literature.

Sect. Pg. Acetylenes Carboxylic acids 3 0 A 21 Alcohols, phenols 45A 56 Aldehydes 60A 85 Arnides 90A 148 Amines 105A 172 Esters Ketones 180A 291 Olefins 210A 333

lPROTECTlONl

INDEX, DIFUNCTIONAL COMPOUNDS Sections-heavy Pages-fight

type

type

302 313 323 337

343

353

338

345

357

346

360

316 326

306 317 327 336 344 351 357

-338 348

307 340

348

361

386

328 337 365

321 331 340

311

351

375

388 322 332 341

396

398

401

412

405

413

/

352 358 363 441

450

355 361 366 370 373 375 407

422

444

349 356 362 867

454

467

371. 374

489

376 377

Blanks in the table correspond to sections for which no examples were found in the literature.

X

INTRODUCTION Relationship between Volume 3 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 3 presents over 1000 examples of published methods for the preparation of monofunctional compounds, updating the 4000 in Volumes 1 and 2. In addition, Volume 3 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 the two 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 chain-lengthening processes before degradations. 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, PhCH20H -+ PhCOOH and PhCH= CHCH20H -+ PhCH =CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Entries in which conjugate reduction or alkylafion 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 exarnpfe, RCH,-H + RCH,COOH (carboxylic acids from hydrides), RMe -+ RCOOH (carboxylic acids from alkyls), RPh -+ RCOOH (carboxylic acids from aryls). Note the distinction between R2C0+ R2CH, (methylenes from ketones) and RCOR' + RH (hydrides from ketones). Alkylations which inxi

INTRODUCTION

xii

volve additions across a double bond are found in section 74, Alkyls from Olefins. The following examples illustrate the application of the classification scheme to some potentially confusing cases: RCH =CHCOOH + RCH = CH, RCH=CH2 + RCH=CHCOOH ArH + ArCOOH ArH + ArOAc RCHO -+RH RCH-CHCHO + RCH=CH2 RCHO + RCH, RZCHZ -+ RPCO RCH2COR + RZCHCOR RCHzCH2 -+ RCHZCH, RBr+RC=CH -+ R C z C R

+

ROH RCOOH + RCOOR RCH=CHCHO -+ RzCHCH2CHO RCH =CHCN -+ RCHZCH2CN

(hydrides from carboxylic acids) (carboxylic acids from hydrides) (carboxylic acids from hydrides) (esters from hydrides) (hydrides from aldehydes) (hydrides from aldehydes) (alkyls from aldehydes) (ketones from methylenes) (ketones from ketones) (alkyls from olefins) (acetylenes from halides; also acetylenes from acetylenes) (esters from alcohols; also esters from carboxylic acids) (alkyls from olefins) (alkyls from olefins)

Yields quoted are overall; they are occasionally reduced to allow for incomplete conversion and impurities in the product. Reactions not described in the given references, but required t o complete a sequence, are indicated by a dashed arrow. 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 investigated from 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. ix, which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes; Section 2, acetylenes from carboxylic acids; and so forth. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of the index. Thus Section 1 gives examples of the reactions of acetylenes that form other acetylenes: Section

INTRODUCTION

xiii

16, reactions of acetylenes that form carboxylic acids: and Section 31, reactions of acetylenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, transposition are found in Sections 1, 17, 33, and so on, which lie close to a diagonal of the index. These sections correspond t o such topics as the preparation of acetylenes from acetylenes, carboxylic acids from carboxylic acids, and alcohols and phenols from alcohols and phenols. Alkylations which involve conjugate additions across a double bond are found in section 74, Alkyls from Olefins. Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 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. ix. The pairs of functional groups alcohol, ester; carboxylic acid, ester: amine, amide; carboxylic acid, amide can be interconverted by quite trivial reactions. When a member of these groups i s the desired product or starting material, the other member should, of course, also be consulted in the text. A few reactions already presented in Volumes 1 and 2 are given again in Volume 3 when significant new publications have appeared. In such cases the starting material and product are shown in a contracted form: for example, ROH instead of PhCH2CH20H. 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 t o 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, 1,3-aminoalcohols and 1,4-arninoalcohols are included in a single section. It is recommended that the following

INTRODUCTION

xiv

illustrative examples of the classification of difunctional compounds be scrutinized closely.

Dif unctional Product

Section Title

RCrC-C-CR RCH(0H)COOH RCH(COOH)CHzCOOMe RCH(0Ac)COOH RCH = CHOMe RCH (OM e)2 RCHF2 RCH( Br)CH,F RCH(OAc)CH20H RCH(0H)COOMe RCOCOOEt RCOCHZOAc RCH = CHCH,COOMe RCH =CHOAc RCH(B r)COOEt RCH(Br)CH,OAc RCH =CHCH$H =CH2

Acetylene-Acetylene Carboxylic Acid-Alcohol Carboxylic Acid-Ester Carboxylic Acid-Ester Ether-Olef in Ether-Ether Ha Iide- Ha Iide Ha I ide-Hal ide Alcohol-Ester Alcohol-Ester Ester-Ketone Ester-Ketone Ester-Olefin Ester-Olef in Ester-Halide Ester-Halide Olefin-Olefin

How t o Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. x gives the section and page corresponding t o each difunctional product. Thus Section 327 (Alcohol-Ester) contains examples of the preparation of hydroxyesters; contains examples of the preparation Section 323 (Alcohol-Alcohol) of diols. Some preparations of olefinic and acetylenic compounds from olefinic and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, RCH =CHBr -+ RCH -CHCOOH, Carboxylic acids from Halides (monofunctional sections) 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 t o the preparation of

INTRODUCTION

xv

diols by using the corresponding dichloro compound as a starting rnaterial. 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, arnide; 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, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 1

PREPARATION

OF ACETYLENES

Section 1

PhCzCH

Acetylenes from Acetylenes

1) BuLi

PhCzCBu

P

2 ) Bu3B

80%

3 ) MeSOCl

T e t r a h e d r o n (1974)

HCmCCH20H

1 ) LiNH2, NH3

PhI

21 59

n-C6H1 3-CKCH20H

2 ) n-C6H13Br

JOC USSR (1975)

PhCeCH +

30

(Ph3P)* PdC12/CuI

*

60%

11 517

P hCKP h

90%

Et2NH

T e t r L e t t (1975) 4467

PhI

+ E-PrCzCH

Pd( PP h 3 I 4 +

NaOMe, DMF

PhCEC-n-Pr J Organometal Chem (1975)

97%

93 253,

259

2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

[Bu3BCzCPh]Li

12

BuCtCPh

85% JOC (1974)

-i-BujB

+ LiCtCCl

SECTION 1

1 ) I23 -78"

2

731

-i-BuCEC-Bu-i-

2 ) NaOH/H202

85%

Tetr Lett (1975) 1961

+ LiCSCHC5H11

I OR

2) I *

OR

JOC (1976)

+u

1 ) THF

Sia2BCrC

2) I 2

LiC=CCMe3

t-BuC1

65%

__3

+

0-

CfC-CzC-CMe 3

F

JOC (1976)

CH2Cl (BtiCeC)3Al

7

0"

41 3947

70%

5 1078

t-BuCsC-Bu -

JACS (1975)

97

98% 7385

SECTION 5

Section 2

ACETYLENES FROM ALKYLS, METHYLENES AND ARYLS

Acetylenes from Carboxylic Acids

No a d d i t i o n a l exampl es

Section 3

Acetylenes from Alcohols

No a d d i t i o n a l examples

Section 4

A c e t y l e n e s f r o m Aldeh.ydes

No a d d i t i o n a l examples

Section 5

No examples

A c e t y l e n e s f r o m A l k y l s , Methylenes and A r y l s

3

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

4

Section 6

SECTION 9

Acetylenes from Amides

No a d d i t i o n a l examples

Section 7

Acetylenes from Amides

No a d d i t i o n a l examples

Section 8

Acetylenes from Esters

PhCOOMe

\

fl

\ 0'\"p

llii

/

%35%

Ph

Ph-C-C-Ph

JOC (1976)

Section 9

No

examples

Acetylenes from Ethers

fl 2640

SECTION 10

Section 10

HCBr=CBrH

ACETYLENES FROM HALIDES

5

Acetylenes from Halides

2 eq. Ph2PLi, THF

*

HCaCH

rfx

0CH=CCl

80%

T e t r L e t t ( 1 9 7 5 ) 4709

CrCCl

Et2NLi

80%

E t 2 0 , THF S y n t h e s i s (1975) 458

t

-

ci

F2C=CC1

JOC (1976)

EtOCH(CH2)11Me

I

CH2C1

41 1487

-60 - 80%

BuLi Et20/hexane

HCrC( CH2)1 1CH3, S y n t h Comm ( 1 9 7 5 )

81 %

5

331

6

S e c t i o n 11

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 14

Acetylenes from Hydrides

No examples

F o r examples o f t h e r e a c t i o n R C d H (Acetylene - Acetylene)

S e c t i o n 12

+

RCiC-CrCR'

see s e c t i o n 300

A c e t y l e n e s f r o m Ketones

90%

Chem L e t t (1976) 147

Section 13

Acetylenes 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

No a d d i t i o n a l examples

SECTION 15A

Section 15

PROTECTION OF ACETYLENES

Acetylenes from Miscellaneous Compounds

COOMe

KC1, s u l f o l a n e +

COOMe

crown e t h e r , 150"

NC-CsC-COOMe

T e t r L e t t (1975) 2429

Section 15A

7

P r o t e c t i o n o f Acetylenes

No a d d i t i o n a l examples

16%

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

PREPARATION OF CARBOXYLIC ACIDS ACID HALIDES AND ANHYDRIDES

Chapter 2

S e c t i o n 16

Carboxylic Acids from Acetylenes

H- C =C -OEt /OEt H3C-C-OPh ‘0Ph

+ PhOH

75%

Rec Trav C h i m (1975) Also v i a : Esters - S e c t i o n 106, Amides - S e c t i o n 76. D i f u n c t i o n a l Compounds.

S e c t i o n 17

94 209

Also see any r e l e v a n t

Carboxylic A c i d s , Acid H a l i d e s and Anhydrides from Carboxyl ic Acids

fH3 CHZ=C-C02Li

+ CH3CH(Li)C02Li

r

CH2(CHC02Li)2

66%

I

2. H20

CH3 Gazz C h i m I t a l (1976)

a

106 201

SECTION 1 7

b

O

CARBOXYLIC A C I D S , A C I D H A L I D E S AND ANHYDRIDES FROM CARBOXYLIC A C I D S

O

1 ) 2 LDA, THF

H

9

99%

2) Me1

Gazz Chim I t a l (1974)

Me3SiCH2COOH

1 ) 2 LDA

104 6 2 5

M e 3 S i CHCOOH

;

8 7%

I

2) ~ - 6 ~ 1

Bu

JCS Chem Comm (1975) 5 3 7

PhSCH2COOH

1 ) 2 LDA

+

2) i - P r I

PhSCH-COOH

99%

I

i-Pr J C S C h e m Comm (1975) 714

MeSCH2COOH

1 ) LDA ).

2) i - B u B r

MeSCHCOOH

80%

I

T e t r L e t t (1975) 3 7 9 7

*

1 ) E t L i , THF, - 7 8 "

Ph-CHCH2COOH

P hCH: C H-

I Et

2 ) MeOH 3) H30f

(high o p t i c a l yield) JACS (1975)

97 6 2 6 6

66%

10

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

1 ) LDA 2)

r

BuI

B'\

'

H3C

-78"

3) H30t

SECTION 17

H'

70% y i e l d 40-80% o p t i c a l y i e l d s JACS (1974) 96 6508 JOC (1974) 3 r 2 7 7 8 T e t r L e t t (1974) 3495

Med

42% y i e l d 75% o p t i c a l p u r i t y JACS (1974) 96 268, 6508 JOC (1974) 2 618, 2778

1) PhLi 2 ) H30

'

70%

t

OMe

OMe JACS (1975)

97

7383

11

CARBOXYLIC ACIDS, ACID HALIDES AND ANHYDRIDES FROM CARBOXYLIC ACIDS

SECTION 17

Ph

M e o H\\'Y' C O O H

1 ) BuLi 2 ) H30+

Me0

65%

R

Me0

S 81% e e

T e t r L e t t (1976) 1947

Ph

MeCHz*$:

1

1 ) LDA 2) BuI

b

3 ) H30'

CH20CH3 JACS (1976)

Me

Et

\

iieOMe 2)

H30

'

Me'x

92%

Buco

H

'66% e e

98 567

Et

H

:'?,,,, ,g

86% 34% e e

Me

JACS (1976)

3 2290

Carboxylic Acids may be a l k y l a t e d and homologated via k e t o a c i d , k e t o e s t e r and o l e f i n i c a c i d i n t e r m e d i a t e s . See s e c t i o n 320 (Carboxylic Acid - Ketone), s e c t i o n 360 ( E s t e r - Ketone) and s e c t i o n 322 (Carboxylic Acid - O l e f i n ) . Conjugate reductions o f unsaturated a c i d s a r e l i s t e d in S e c t i o n 74 (Alkyls from O l e f i n s ) .

12

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 3

PhCOOH

SECTION 17

H

Ph-Y-Cl

t

90%

CC14 JCS Chem Comm ( 1 9 7 5 ) 622

Polymer-PC1

RCOOH

RCOCl JACS ( 1 9 7 4 )

96 6469

0 0

0 0 +

II I1

CH3-C-C-C1

54%

S y n t h e s i s ( 1 9 7 5 ) 163

80-95% JACS ( 1 9 7 4 )

96 925

Ph

i=\

ph+

COOH

If-'

0 Et3N Chem L e t t (1976) 303

SECTION 19

13

CARBOXYLIC A C I D S AND ANHYDRIDES FROM ALDEHYDES

70% Synthesis (1975) 801

S e c t i o n 18

PhH

C a r b o x y l i c Acids from A l c o h o l s

+ aq. KMn04 +

0 0

Bu4NBr

-

" P u r p l e Benzene"

PhCH20H

PhCOOH

T e t r L e t t (1974) 1511

S e c t i o n 19

C a r b o x y l i c Acids and Anhydrides from Aldehydes

74%

Synthesis (1976) 807

SECTION 21

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

14

Ph-CHO

MedNF: t

Ph H

Ph

1) EtLi _L

2 ) H30@

2 ) MeOH

3) H30'

0Me

Owe JACS (1975)

px Et

CH2COOH

66% 97% ee

97 6266

Related methods: C a r b o x y l i c Acids f r o m Ketones ( S e c t i o n 27). Also via: Esters - S e c t i o n 105, Amides - S e c t i o n 79. Also see any r e l e v a n t Difunct i o n a l Compounds.

Section 20

Carboxylic Acids from A l k y l s

No a d d i t i o n a l examples

Section 21

Carbox.ylic Acids from Amides

0

It

Ph-C-NH2

"20

NaOOH 50-80"

85%

PhCOO

JOC (1975)

9 1187

15

CARBOXYLIC ACIDS FROM ESTERS

SECTION 23

0 2 , CH30H

P h - CNHN H 2

*

Cu( OAc )

PhCOOH

9 5% Chem L e t t (1975) 437

C a r b o x y l i c A c i d s , A c i d H a l i d e s and Anhydrides f r o m Amines

S e c t i o n 22

No a d d i t i o n a l examples

Carboxylic Acids from Esters

S e c t i o n 23

R

0

II

BBr3

R-C-OR'

R-C-OH

R ' = Me, E t , t - B u , PhCH2, e-NOZ-PhCH2

JOC (1974)

C7H15C00-t-Bu

-

1 ) K02-crown e t h e r 2) H30@

1427

96%

C7HI5COOH

JOC (1976)

R-COOCH3

2

5 586

KH, OMSO

63%

RCOOH

RCOOCH3 = m e t h y l podocarpa-8,11,13-trien-19-oate Synth Comm (1976)

6

469

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

16

SECTION 23

74%

2

Synth Comm (1975)

305

0

COOH

\-OBZ

90% Angew I n t

Ed (1976)

774

AcOH

85%

quinoline,

Me

COOH

Synthesis (1975) 330

PhCH2C02Me +

LiI

PY r ---+

PhCH2C02Li

Org React (1976)

93%

2

187

SECTION 25

CARBOXYLIC ACIDS FROM HALIDES

17

Me

80%

KMe Me JACS (1976)

98 2868

2 MeA1C12

91%

‘sHl

Me

3

S e c t i o n 24

Me

J P r a k t Chem (1974)

316

215

Carboxylic Acids from Ethers

No a d d i t i o n a l examples

S e c t i o n 25

C a r b o x y l i c A c i d s from H a l i d e s

Br

-

COOH

1 ) BuLi 2)

cop

S y n t h e s i s (1974) 443

97%

18

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

PhCUMgX2

1 ) (Et0)3P, Et20/HMPA +

SECTION 25

PhCOOH

9 5%

2) co2

3) H@

J Organometal Chem (1975)

94 463

R = Bz, Ar, v i n y l , h e t e r o c y c l i c Organometal Chem (1976) j 2 J

J

Me

Me-Br

1 ) B$46

Ph

Br

I

Ph-CH-COOH

+

45%

2 ) Cr03/H2S04

Synth Comm (1976)

"

-PPh3

R'

1 ) cop 2 ) @OH, H20 3) H30@

C55

6

349

R

COOH

*

80-90%

R'

T e t r L e t t (1974) 1275

A l s o v i a : Esters - S e c t i o n 115, Amides D i f u n c t i o n a l Compounds.

-

Section 85.

Also see any r e l e v a n t

SECTION

27

S e c t i o n 26

CARBOXYLIC ACIDS FROM KETONES

19

Carboxylic Acids froni Hydrides

CH2( COO@),Na,

Ph-OCH3

55%

PdCT2, AcOH OCH3

JOC (1976)

(CH2)3CHCOOH

I

NHR

I

1)

C1-COOEt

2) CH2N2 !-

NHR

41 2049

3 ) AgOCOPh 4 ) O' H

NHR

NHR

0

il

R = PhCH20C-

o r 1-BuOC-

II 0

Also v i a :

S e c t i o n 27

B u l l Chem SOC Japan (1975)

48

2401

E s t e r s ( S e c t i o n 116)

C a r b o x y l i c A c i d s f r o m Ketones

97% JCS P e r k i n I (1974)-927

20

Also via:

S e c t i o n 28

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

Esters

-

S e c t i o n 117.

SECTION 30

See a l s o r e l e v a n t D i f u n c t i o n a l Compounds.

Carboxylic Acids 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 29

C a r b o x y l i c A c i d s from O l e f i n s

B u l l Chem Soc Japan (1976) 49 3296

S e c t i o n 30

C a r b o x y l i c A c i d s f r o m M i s c e l l a n e o u s Compounds

Review: "Syntheses of T e t r a c a r b o x y l i c A c i d s " Russ Chem Rev (1973)

42 939

PROTECTION OF CARBOXYLIC A C I D S

SECTION 30A

S e c t i o n 30A

P r o t e c t i o n o f Carboxylic Acids

Ph2C=NNH2

R-COOH

21

i

+

>go%

R-C-OCHPh2

12, AcOH

U s e f u l f o r p r o t e c t i n g amino a c i d s

3 C S P e r k i n I (1975) 2019

0

0

II

c-OBZ

1 ) cuso4 2 ) EDTA

+

Q74% JOC (1975)

3

JOC (1975)

40 2962

3287

PhCH20CH2C1

0

II

R-C-ONa R-COOH

or H2, Pd/C

COOH

1) C u / Q u i n o l i n e , 200"

70%

2 ) CH30H HOOC

S y n t h e s i s (1976) 40

COMPENDIUM OF ORGANIC SYNTHETIC METHODS V O t 3

22

A R

A

Zn, THF/H20

Ph-CNHCH2C-OCHZCC1

SECTION 30A

P h-CNHCH2COOH

pH 5.5

83%

Synthesis (1976) 457

il

Ph-C-OCH2CH2Cl

Co( 1)phthalocyanine

r

PhCOOH

66%

Angew I n t Ed (1976)

3

681

Use of t h e t r i m e t h y l s i l y l group t o p r o t e c t t h e carboxyl f u n c t i o n o f penic i l l i n s u l f o x i d e s d u r i n g t h e i r conversion t o deacetoxycephalosporins.

JOC ( 1 975)

.(

H@

2 1346

( s t a b l e t o carbanions)

JOC (1974)

2 2787

SECTION 30A

PROTECTION OF CARBOXYLIC ACIDS

23

CH200CPh

CH2C1

i

I

'CH3S

@

JACS (1974)

96 590

Use of TlOR t o cleave p r o t e c t e d p e p t i d e s from M e r r i f i e l d r e s i n . Can J Chem (1974)

52 2832

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 of carboxylic a c i d s a r e included i n S e c t i o n 107 ( E s t e r s from Carboxylic Acids and Acid Halides) and Section 23 (Carboxylic Acids from E s t e r s ) .

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 3

PREPARATION OF ALCOHOLS

AND PHENOLS

Section 31

Bu3B

A l c o h o l s from A c e t y l e n e s

1 ) LiCrCH 2) aq. HC1.

CH3C( Bu) 20H

F

A

JOC (1975)

3) NaOH, H202

1) Bu2BH MeCECEt

BU

2 ) MeLi f

3 ) HC1 4)

40 2845

NaOH/H2OZ

1

MeCH2C -E t

70%

I

OH S y n t h e s i s (1974) 339

24

SECTION 32

ALCOHOLS FROM CARBOXYLIC A C I D S

S e c t i o n 32

25

A l c o h o l s from C a r b o x y l i c A c i d s

00

Bu4N BH4

PhCOCi

>

PhCH20H

100%

JOC (1976)

CH2CHCOOH

Me0

* BIr

NH2. HC1

------'ZH6

ffl 690

Ar-CH2CHCH20H

I NHjHCl

THF

80%

JCS P e r k i n I (1974) 191

PhCOOH

+ BH3.MeSH

+

B(OMe)3

-

PhCH20H

JOC (1974)

RCOOH

+

Ph

1) Et3N

3

3052

RCH20H

t

2 ) NaBH4 JOC (1974)

39

111

80-100%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

26

1 ) BuLi, -100' CH2C1

&-

2 ) PhCOC1, -78" 3 ) MeOH/HOAc

PhC-(CHC12)2

I

OH Chern B e r (1975)

Also via:

108 328

E s t e r s ( S e c t i o n 38)

S e c t i o n 33

A l c o h o l s from A l c o h o l s and Phenols

Org Synth (1976)

S e c t i o n 34

55

1

A l c o h o l s and Phenols from Aldehydes

2 Ph-OMgBr

+

PhCHO

benzene

JCS Chem Comm (1976) 309

SECTION 34

SECTION 34

RCHO +

27

ALCOHOLS AN0 PHENOLS FROM ALDEHYDES

E t20/HMPA

MepCuLi

>go%

RCHOHMe

+

(Me0 13P

T e t r L e t t (1975) 2353

Me3Si CH2CH=CH2

CH3( CH2) 2CH0

T i C1

CH2C1

dH T e t r L e t t (1976) 1295

PhCHSH

1 ) BuLi PhCH2SH

-

1 I

70%

CH(OH)

2) PhCHO

Ph Angew I n t Ed (1974)

Me2NCH2CO2-L-Bu

1 ) LDA, -78" 2) CH3CH0

r

2 202

CH3CH (OH) CHCO2-L-Bu

8 5%

I

NMe2 T e t r L e t t (1975) 1477

PhCHO

+'& '0

-

1 ) TiC14, CH2C12

2) MeOH

PhCH( OH)CH2COCH2

t

COOMe Chem L e t t (1975) 161

91%

SECTION 34

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

28

MeCOCCl

I ) LDA, THF, -75" 2 ) EtCHO

MeCOCCl

f

73%

I CH( OH) E t

Bull SOC Chim France (1975) 1876

MeN (NO )Me

1 ) LDA, THF, -80"

+

MeN( NO)CH2CH(0H)Ph

85%

2) PhCHO Chem Ber (1975)

I ) LDA

/ NMePh

MeCH=C C' N

2) PhCHO

t

1293

,NMePh PhCHCH2CH=C

I

81 %

C' N

OH

Syflthesis (1975) 512

PhCHO + n-Bu3SnCC13

1) 80" 2 ) H20

PhCHOHCC13

63%

J Organometal Chem (1975)

Cl3CC0 - i - P r 2 -

1 ) Et2NLi, THF-OH-HMPA 2 ) Me2CHCH0

t

102

Me2CHCHCC l2COz-I-Pr

I

OH Synthesis (1975) 524, 533

423

77%

SECTION 34

1 ) LDA, THF/Et20, -90"

CH2Br2

29

ALCOHOLS AND PHENOLS FROM ALDEHYDES

PhCH-CHBr2

+

63%

I

2) PrCHO

OH

B u l l SOC Chim France (1975) 1797

PhCHO + CHC13

t-BUOK, NH3. -75"

84%

PhCH-CC13

I

OH J Gen Chem USSR (1974)

PhSCH2SePh

t

2 ) PhCHO

44 2590

94%

PhSCH2-CHPh

I

OH

T e t r L e t t (1975) 1617 Angew I n t Ed (1975)

14 350,

700

Li

I

PhSe(0)CHCH2CH2Ph

+ EtCHO

A

87%

PhSe( O)CHCH2CH2Ph

I

HC (OH) E t

JCS Chem Comm (1975

(E-C

) BC1 6 13 2 H

+ BuC=N-&-Bu

I

Li

1) Et20, -78" 2 ) HSCH2COOH

'

(!-C6H

3 ) NaOH, d i g l y m e 4 ) NaOH, H202

JOC (1975) 3 3644 T e t r L e t t (1975) 2689

790

87%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

30

SECTION 34

CH20H Ra-Ni (Cr-promoted)

88%

Et3N, KOH, MeOH

T e t r L e t t (1976) 4681

Me2CHOH

CH20H

a1 umi na

CHO

82%

p&

+

T e t r L e t t (1975) 3601

FeCl SNaH c

THF

CHO

CH20H Chem L e t t (1976) 581

RCHO

+

EtgSiH

H0

RCH20H JOC (1974)

3 2740

Benzaldehyde i s reduced i n preference t o acetophenone by NaBH(OAc)3. JCS Chem Comm (1975) 535

SECTION 34

L i A 1H ( 0-&- B u )

NaBH4

ALCOHOLS AND PHENOLS FROM ALDEHYDES

31

reduce benzaldehyde i n t h e presence of acetophenone, and b u t a n a l i n t h e presence of 2-butanone.

LiBH4 Aust J Chem (1975) g 3 1383

4

CH20H

SnH

-n-B u

78%

CHO

CHO

JOC (1975) @ 1966

60-90%

JCS P e r k i n I (1974) 1353

(c)>cH

1 ) MeLi-THF 2 ) PhCHO

r

PhCH20H

3) NaHC03, H202 JACS (1975)

97 5608

97%

32

COMPENDIUM

Related methods:

S e c t i o n 35

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 38

Alcohols from Ketones ( S e c t i o n 42)

Alcohols and Phenols from A l k y l s , Methylenes and A r y l s

No examples of 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 ROH ( R = a l k y l o r a r y l ) see 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 Section 41 (Alcohols and Phenols from Hydrides). -f

S e c t i o n 36

Alcohols and Phenols from Amides

No a d d i t i o n a l examples

S e c t i o n 37

Alcohols and Phenols from Amines

No a d d i t i o n a l examples

S e c t i o n 38

P h- C- OMe

Alcohols from Esters

NaBH4, HSCH2CH2SH r

PhCH20H

THF, r f x 20 h r s . T e t r L e t t (1975) 3295

100%

ALCOHOLS AND PHENOLS FROM ETHERS AND EPOXIOES

SECTION 39

Na@[OBH 3C ( CH3) NPh

PhCH2CH2COOEt

p

Ph(CH2)30H

CH2C1

97%

Chem Pharm B u l l (1976)

&NHCHRCOOE

t

33

41059

NHCHC-R'

1 ) 3 eq R'MgX

R OH

2 ) H20

"excellent yield" Comptes Rendus

R e l a t e d methods:

S e c t i o n 39

C (1975) 280 123

C a r b o x y l i c A c i d s f r o m E s t e r s - S e c t i o n 23, P r o t e c t i o n o f Alcohols - S e c t i o n 45A

A l c o h o l s and Phenols f r o m E t h e r s and Epoxides

H I , NaI

OMe

+

84%

CH30CHC12

OH

JOC (1976)

41 367

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

34

SECTION 39

JCS P e r k i n I (1976) 2237

A d d i t i o n a l examples o f 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 o f Alcohols and Phenols).

PhCH2CHOHCH2Bu

PhCH2CHOHCH2Et

NaAl E t 4

T e t r L e t t (1975) 2521

LiEt3BH THF

+

&:

HO

OCOPh T e t r L e t t (1976) 3775

SECTION 39

EPOXIDES

ALCOHOLS AND PHENOLS FROM ETHERS AND

0

Li

35

0

PhCH2CH20H

t

99%

JCS Chem Cornm (1976) 672

n VS Li

+

@> OH

98%

Used i n j u v e n i l e hormone s y n t h e s i s . JOC (1974)

Me3Si

Bu2CuLi Et20, -25"

F

39

3645

BuCH(Si Ve3)CH20H

JOC (1975)

5

2263

88%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

36

SECTION 39

Me3A1

90%

130"

J Organometal Chem (1974)

+

(CH3)2CuLi

-

73 187

CH3CHOHCH2CH3

Org React (1975)

89%

2 253

4) H

LOA

Et20/hexane

H

80%

OH

S y n t h e s i s (1975) 602

1 ) Et2NH, L i , MeC=N

HMPA/ benzene

I Pr

n-PrCOCH2CH2CH( 0H)Et

Et S y n t h e s i s (1975) 256

95%

SECTION 40

S e c t i o n 40

ALCOHOLS AND PHENOLS FROM HALIDES AND SULFONATES

37

A l c o h o l s and Phenols f r o m H a l i d e s and S u l f o n a t e s

R w c 5 H 1 1 CH3S020 6

KO2, crown e t h e r DMSO/DMF/DME

R

75%

3

T e t r L e t t (1975) 3183

* ‘gH1 3-CHCH3 ITS

1 ) KO2, DMSO, crown e t h e r

*

3-iHCH3

F

2 ) H20

OH

(R)

(S)

JOC (1975)

RBr

75%

+ HgC104 + H20

-----.A

40 1678 64-98%

ROH

21 cases T e t r a h e d r o n (1974)

n-BuSnCH20H

1) 2 2-BuLi 2 ) n - o c t c1

30 2467

n-Oct-CH20H Angew I n t Ed (1976)

15 438

38

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

,,B~

1) Ph2POMe, CHCl

VOL 3

CH20H

25"

80-90%

2 ) t - B u L i , THF-Et20. R

R'O

3 ) CH20, ZnC12,

THF, -78'

R

JACS (1975) 97 4745, 6260

MeHBr 2) H-0,.

NaOH

Me

I

97%

P hCHCH20H

S y n t h Comm (1976)

S e c t i o n 41

SECTION 41

a 349

A l c o h o l s and P h e n o l s f r o m H y d r i d e s

Fe",

Cut+

Ph-OH JACS (1975)97 1603

JCS Chem Comm (1975) 36

64%

SECTION 41

39

ALCOHOLS AND PHENOLS FROM HYDRIDES

51% y i e l d

11% conversion

J O C (1976)

41 2651

72%

J O C (1975) Q 2141

Y

1 ) LDA, THF 2)

Yo"

+

+30%

o2

OOH

3) H30+

J O C (1976)

fl 370

OH I

Rec Trav C h i m (1976)

95

285

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

40

Review:

SECTION 42

Photochemical H y d r o x y l a t i o n o f Aromatic Compounds S y n t h e s i s (1974) 173

S e c t i o n 42

A l c o h o l s f r o m Ketones

JOC (1976) 1 3 2 0 9

Me2C0

+ BrCH2CMe=CHCOOEt

1 ) Z n , HgJ2

t

Me#( OH)CHCMe=CH2

I COOEt

2) 3 ) H@

J Organometal Chern (1975)

70%

96 149

H

MeLi -Me2CuLi

91%

E t 2 0 , -70"

( h i g h y i e l d a x i a l OH) JACS (1975)

97 5280

SECTION 42

41

ALCOHOLS FROM KETONES

JCS Chem Comm (1975) 892

f e t r L e t t (1975) 3897

Review:

S t e r e o c h e m i s t r y o f O r g a n o m e t a l l i c Compound A d d i t i o n t o Ketones Chem Rev (1975)

75 521

T e t r L e t t (1975) 1811

42

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

LiAl (E-B~)~OR

YH3 P h -C -E- Bu

+

PhCOCH3

SECTION 42

I OH

R = (-)-N-methylephedrine

56%

31% ee T e t r L e t t (1976) 4781

1 ) BuLi, THF-hex.

I

91 %

2) Ph2C0

I

Me

Me

JOC (1975) 3 1342

S y n t h e s i s (1975) 333

1 ) t - B u L i , E t 2 0 , -78" B r AOMe

2)

0

0

'

%

Me0

T e t r L e t t (1975) 3685

92%

SECTION 42

43

ALCOHOLS FROM KETONES

6ph

Ph 1) BuLi, -100" 2) PhCOPh

*

CN

JOC (1976)

83%

CN

41 1187

S y n t h e s i s (1975) 705

OH MeCOCH=CH2

II

NaCXH, MgS04

Me -C C=CH

l i q NH3/Et0

CH=CH2 Can J Chem ( 1 975)

CH3COS-t-Bu

1) LDA, -78"

2 ) Ph2C0

70%

b

53 2157

Ph2C (OH) CH2COS-L-Bu

T e t r L e t t (1975) 3255

80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

44

1 ) L i . THF

Et-C(Me)C02-i-Pr

I c1

2) (CH3)*CO

SECTION 42

Me

I

EtC-CO2-L-Pr

b

71 %

I

Me2COH J Organometal Chem (1975) 102 129

1 ) LiNH2, liq NH3

NCCH2CH2COOH

2)

Ph2C0

I-

Ph2C-CHCH2COOH

61%

I 1

OH CN

J Organometal Chem (1975) 92 125

PhCCH3

Et

1) NaA1Et4, NiC12

r

2 ) NH4C1

I

Ph-C-CH3

84%

I

OH Tetr Lett (1976) 993

Bull Chem SOC Japan (1976)

PhZCO

Me3A1 N i (acac)2

+

Ph2COH

9 3646

58%

I Me

Aust J Chem (1974)

2569

SECTION 42

45

ALCOHOLS FROM KETONES

JOC (1975)

b

40 593

Me3SiCH2CH=CH2

70%

TiC14, CH2C12 T e t r L e t t ( 1 9 7 6 ) 1295

Me CH2=CHCH2TMS +

MeCOCH2C1

I

1 ) GaC13

I

2 ) MeOH

CH2C1

J Organometal Chem (1975)

NaH Ph

CH3

FeCl

60%

C-OH

----+

c

JOC (1976)

Ph

41 1667

93 43

72%

6 =-Oa

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

46

L i A1 H2R2

c

SECTION 42

70%

-4

R

J O C (1975)

b

40 926

80

Bu4N BH4

98%

CH2C1 JOC (1976)

41 690 OH

0

II

Ph/'\Cti3

KBH4, H20/benzene

I

Ph-CHCH3

. !

phase-transfer c a t a l y s t

97%

Synthesis (1975) 531

L i Sia3BH

99%

THF, -78" CH3 J A C S (1976)

98

3383

SECTION 42

ALCOHOLS FROM KETONES

47

84%

90%

JACS (1976)

KHB (s-Bu

98 1965

)

HO

THF

JOC ( 1 9 7 5 )

40 146

48% 17% ee Tetr

Lett ( 1 9 7 6 ) 295

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

48

t

t

H2

RhH2 [PPhMe2]2(Solvent)2 catalyst

-

Org React (1976)

Ph\

Ligand

CH<

-

-OH 86% 1

*

H2(50 atm)

c=o

3

SECTION 42

96%

PhCHCH3

I

Rh@/MeOH

OH R 43% ee

Y

Ligand

=

M e,

q’:GN

Me2

PPh2

[Rh]*

R /‘\Ph

R

=

1”,2’,3”

T e t r L e t t (1976) 4351

catalyst

MeOH, NaOMe alkyl

R H :‘O -H Ph’ up t o 58% ee

J Organometal Chem (1976)

122 83

SECTION 42

ALCOHOLS FROM KETONES

49

0

II

Ph-C-CF3 ( S ) 68% ee S y n t h e s i s (1975) 701

4

H

A1 C1

0’

( v a r i o u s 3-0x0 tr it e r p e n o i ds )

Me0

HO

4

75-100% a x i a l a l c o h o l

JCS P e r k i n I (1976) 321

JOC (1976)

41 3624

2.70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

50

SECTION 42

IIlIOH RaNi

95%

NaOH/EtOH Synthesis (1975) 702

@ \

I

1 ) Et2NOH

83%

2) H30@

OH

0

T e t r L e t t (1975) 1695

b0

+ H2S04

1 ) Ac20, AcOH 2 ) H30@

95% OH

P"

0

same conditions

95%

&OH JOC (1974)

Related methods:

3

3697

Alcohols from Aldehydes ( S e c t i o n 34)

SECTION 44

S e c t i o n 43

51

ALCOHOLS FROM OLEFINS

A l c o h o l s and Phenols f r o m N i t r i l e s

1) LiNEtq

9 0%

2) C1 CH2CH20THP

3) Na, t-BuOH, HMPT

4 ) H306 S y n t h e s i s (1976) 391

S e c t i o n 44

Alcohols from Olefins

F o r t h e p r e p a r a t i o n o f d i o l s f r o m o l e f i n s see S e c t i o n 323 ( A l c o h o l - A l c o h o l )

'OH,

H202

J-

cyclohexanol JACS (1975)

97 5249

90%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

52

/

1 ) BH3 2 ) C' N

--

0 Hex3BCN

1 ) TFAA 2) O ' H,

Hex3COH

H202

SECTION 44

96%

JCS P e r k i n I ( 1 9 7 5 ) 1 3 8

(n-hexyl)3B

+

1 ) HSC12

R'C(SR")2

(-1

r

2 ) H202, O' H

(fi-hexyl)2C-OH

I

-80%

R'

JCS Chem Comm ( 1 9 7 4 ) 863

Use ofBH3-Me2S as a h y d r o b o r a t i o n a g e n t .

JOC ( 1 9 7 4 )

2

1 ) LiCH2SMe

1437

CH20H

97%

2 ) Me1 3 ) NaOH, H202 JOC ( 1 9 7 5 ) $ 8 1 4

1 ) LiCH=CH2 R3B

2 ) HC1, - 7 8 " 3 ) NaOH, H202

t

87-94%

R2C-Me

I

OH JACS ( 1 9 7 5 )

97 5 0 1 7

(C6H13)3B

53

ALCOHOLS FROM OLEFINS

SECTION 44

00

+

Me3N-0

w

R’

R3

R2

R4

-

-

95%

3 C6H,30H

1 ) NaBH4, AcOH/THF

2 ) NaOH, H20. H202

R1 R3

R 2 -C-CH-R4 1 I

I

OH Simp1 i f i e d h y d r o b o r a t i o n procedure S y n t h e s i s (1974) 340

Review:

Thexylborane, A H i g h l y V e r s a t i l e Reagent f o r Organic S y n t h e s i s v i a Hydrobora t ion S y n t h e s i s (1974) 77

Review:

Organoboranes as Reagents f o r O r g a n i c S y n t h e s i s Chem SOC Rev (1974)

3

F u l l e x p e r i m e n t a l d e t a i l s f o r p r e p a r a t i o n and use o f 9-BBN as a h i g h l y s e l e c t i v e r e a g e n t f o r h y d r o b o r a t i o n o f o l e f i n s .

JACS (1974)

96

7765

443

54

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 44

76%

3) H30' T e t r L e t t ( 1 9 7 5 ) 3041

RCH=CH2

ArSH

02' hu

F

A

R-CH-CH2-S-Ar

I

OH JOC ( 1 9 7 4 )

+

C13CCH0

54-92%

39

1170

1 ) HgX2

2$ B H F

3 ) Na o r Zn

moderate y i e l d

JOC ( 1 9 7 4 )

39

1474

no

58%

T e t r L e t t (1976) 3783

yield

SECTION 45

55

ALCOHOLS FROM MISCELLANEOUS COMPOUNDS

S e c t i o n 45

0

A l c o h o l s f r o m M i s c e l l a n e o u s Compounds

OH

/

00

PhCH=N

20-94%

X

X = COOR, NO2,

CHO, CONR2

CN, COCH3, JOC (1974)

39

3343

80%

H e l v Chim Acta (1976)

59

2213

77%

3 ) H202, NaOH t-Bu-N=C -

\

Li

T e t r L e t t (1975) 2689

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

56

(L-Hex)$

1 ) HSCH2C02H

+ t-6U-N.C

PBU \

Li

(fl-Hex)2C-OH

I n-Bu

2 ) H202, NaOH

JOC (1975)

SECTION 45A

87%

-

40 3644

94% 3 ) H202, NaOH T e t r L e t t (1976) 2201

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

JACS (1975)

97

1614

SECTION 45A

Synth Comm (1975)

Me

A r - ( cH2 4-

L-I

57

PROTECTION OF ALCOHOLS AND PHENOLS

5 91

Me Ac20, DMSO

u

OH

Me

F

I I

A r - ( CH2)4-C-OCH2SCH3 Me

HgCl 2, CH3CN/H20

T e t r L e t t (1976) 65

ROO + C1CH2SCH3

Na I

ROCH2SCH3

S t a b l e t o base and m i l d a c i d . ROCH2SCH3

Hg"

o r Ag'

ROH

T e t r L e t t (1975) 2643, 3269

90%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

58

OMSO, HOAc, Ac20

\

ROH

R = 1",2",3"

SECTION 45A

ROCH2SCH3

NaHC03fl

alkyl

T e t r L e t t (1976) 3067

-

Use o f t h e 6-methoxymethyl (MEM) group f o r t h e p r o t e c t i o n o f a l c o h o l s . ROH

+

MEM-C1 + ( I - P r ) 2 N E t

0

0

ROH + MEM-NEt3 C1

ROO + MEM-C1

---+

RO-MEM

!'f:'* RO-MEM RO-MEM

MEM = -CH20CH2CH20CH3

S t a b l e t o s t r o n g bases, r e d u c i n g agents, some o x i d i z i n g agents, and m i l d a c i d s . Removed b y ZnBr2 o r TiC14 i n CH2C12. T e t r L e t t (1976) 809

R-OH

+ CH2(0Me)2

R = 1",2"

alkyl

'2'5

ROCH20CH3

S y n t h e s i s (1975) 276

94-99%

PROTECTION OF ALCOHOLS AND PHENOLS

SECTION 45A

0

THF, S0Cl2

RO H

59

Et3N

OR

Removed w i t h m i l d a c i d . T e t r L e t t (1976) 1725

ROH

PhSeCH2CH2Br

ROCH2CH2SePh

AgN03, MeCN

2 ) HC1

Synth Comm (1975)

5

367

4

OCH20CH3

H2C(OMe)2, TsOH

mol. sieves, CH2C12 CHO

2.70%

CHO

Synthesis (1976) 244

NaAl H2(0CH2CH20CH3)2

JOC (1976)

1.50%

41 2545

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

60

el ec trochemica 1 R-O-CH2aOMe

R

=

oxidation

alkyl, benzyl, propargyl, etc.

-n-C8H1./06z

uF6

3

SECTION 45A

ROH + anisaldehyde

74-96%

JOC (1975) 3 1356

69%

-n-C8H170H JACS (1976) 98 6717

--&

Me0 3 H C @ - - S a N Me0

Me0

CHO

Me0 HMPT/Toluene

*

H C @ - - C H O Me0

Synthesis (1976) 191

Further examples of ether cleavages are included in Section 39 (Alcohols and Phenols from Ethers and Epoxides)

90%

SECTION 45A

PROTECTION OF ALCOHOLS AND PHENOLS

61

KF

84%

CH2Br2

T e t r L e t t (1976) 3361

N,N'-carbonyldi imidazole 94%

benzene, r f x . Synth Comm (1975)

5 47

OH, CH2Br2

OH

phase-transfer cat.

82 %

T e t r L e t t (1975) 3489

82% Me T e t r L e t t (1975) 4543

62

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

1

SECTION 45A

hv

Can J Chem (1974) 52 187

Me

I

t-Bu-Si

- - I

Me cannot be used for protecting hydroxy groups in molecules where there i s a n undesired opportunity for acyl migration, e.g. acyl glycerols. JCS Chem Comm (1975) 249

Use of polymer-bound trityl chloride residues to block selectively one primary OH group of a polyhydroxy alcohol iPh2 0-( C H ~ ) ~ - O H

Can J Chem (1976) 54 926, 935

SECTION 45A

PROTECTION OF ALCOHOLS AND PHENOLS

63

Ph c1 I

CH20H @CPh2

p y r i d i ne

HO@oMe

C H Z - O - I ! ~

+

HO4 : : e OH

OH

\HBr

Tetr Lett (1975) 3055

bOMe

Use o f a polymer t o p r o t e c t glucose OH groups:

0

CH2

0'

@CHO TsOH

Ho

-

OH

OH

dioxane JCS Chem Comm (1975) 225

64

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

R-0

n

Pd/C H20 o r MeOH

SECTION 45A

ROH

r

78-95%

R = alkyl, aryl Angew I n t Ed (1976)

15 558

A l l y 1 e t h e r as a p r o t e c t i n g group i n c a r b o h y d r a t e c h e m i s t r y . JCS P e r k i n I (1974) 1446

H i g h l y s e l e c t i v e f o r 1 " OH o v e r 2" OH S t a b l e t o d i l . base, a c i d

3OC (1974)

Use o f (t-Bu)SiMe2 and ( l - P r O ) $ i

39

3767

a s p r o t e c t i n g groups f o r 2 ' , and 2 ' , 5 ' -

p o s i t i o n s o f ribonucleosides.

Tetr Lett (1974) 2861, 2865

SECTION 45A

PROTECTION OF ALCOHOLS AND PHENOLS

65

Use o f HgCl /H S for removal o f the S-trityl group from a-SR 6 lactams 2 2 JCS Chem Comm (1974) 12

RSH = cysteine, glutathione, thiouridine. Chem Pharm Bull (1974) 2 2889

Revi ew : "Photosens i ti ve Protecting Groups"

Israel J Chem (1974)

Review:

"Electro-Deprotection--Electrochemical

12 103

Removal of Protecting Groups"

Angew Int Ed (1976)

281

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 4

PREPARATION

OF

ALDEHYDES

S e c t i o n 46

Aldehydes from Acetylenes

R-CZCH

RCH2CH0

).

2 ) H202, *OH

97

JACS (1975)

H-C*C-C-OCHJ

MeOH

+

5249

( MeO) 2CHCH2COOCH3

NaCN

JOC (1976)

66

41 3765

75%

ALDEHYDES FROM CARBOXYLIC A C I D S AND ACID HALIDES

SECTION 47

S e c t i o n 47

67

Aldehydes f r o m 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 r

RCOOH

. J H e t Chem (1974)

fi 943

1 ) NaBH4

t

PhCHO

___f

87%

2) h y d r o l y s i i JCS P e r k i n I (1976) 323

SH

PhCH=CHCOCl

+ PhNHN=C(SMe)NHPh

1 ) NaBH4

2 ) H30@

PhCH=CHCHO

'

%65%

T e t r L e t t (1974) 2649

R

R-C-C1

-

Ph +

R<@

",N Y 1 SMe N

I Ph

HOAc

+.

RCHO

"20

R = a l k y l , a r y l , cinnamoyl T e t r a h e d r o n (1976)

32

2549

60-90%

68

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

@

Br

I

Br

Et3N

Ph

&cocl 2)

58%

D20 Synth Comrn ( 1 9 7 6 )

"C11H23C-C1

SECTION 47

H2/Pd-C, THF 2,6-1 u t i d i ne

+

6

135

E-C1 H23C-H

95%

Synthesis (1976) 767

PhCOCl

P

PhCOO

JCS Chem Comrn (1975) 459

80%

ALDEHYDES FROM ALCOHOLS AN0 PHENOLS

SECTION 48

S e c t i o n 48

69

Aldehydes f r o m A l c o h o l s and Phenols

C5H5NHCr03C1 CH20H ( p y r chromate) i d i n i u m c h l o r o -'

1'%

85%

CHO

T e t r L e t t (1975) 2647

R-CH20H

Cr02C1 r

R-CHO

May i s o m e r i z e d o u b l e bonds.

-80% JACS (1975)

97 5927

92% S y n t h e s i s ( 1 976) 394

Jones r e a g e n t

-80%

r

CHO

CH20H

JOC (1975)

40

1664

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

70

Ph

CrOg CH20H

SECTION 48

96%

r

resin

CHO

JACS (1976)

98 6737

1 ) TMSCl

JOC (1976)

R-CH20H

Ag2C03 cel i te

I-

41 1479

R-CHO

50-97%

R = pyridine, pyrrole, indole, f u r y l , e t c .

J Het Chem (1976)

PhCH20H

MCPBA

t

JOC (1975)

2 525

PhCHO

40 1860

76%

SECTION 48

ALDEHYDES FROM ALCOHOLS AND PHENOLS

83%

Et3N JOC (1976)

DMSO

Me3C-CH20H

B r2/HMPT

F

fl 957

Me3C-CHO

c

TFAA

81 %

JOC (1976)

Ph-CH20H

71

fi 3329

Ph-CHO

86% S y n t h e s i s (1976) 811

00

PhCHO

B u ~ NBHq

*

CH2C1

PhCH20H

92% JOC (1976)

41 690

00

P h- CH20H

PhCH20H

NO BF4 +

CH2C1

PhCHO

NaOCl tetrabutylammonium b isulfate

62% S y n t h e s i s (1976) 609

>

PhCHO

T e t r L e t t (1976) 1641

76%

72

COMPENDIUM

PhCH20SnBu3

OF ORGANIC SYNTHETIC METHODS VOL 3

NBS

CC14

PhCHO

86%

JACS (1976)

PhCH20H

-

SECTION 48

0 0

I1 il

hv

PhCH20-C-C-CH3

98 1629

PhCHO

95%

‘gH6 S y n t h Comm (1976)

6

281

7 7% JOC (1976)

41 3030

98%

Chem Lett (1975) 691

Ph

1 ) Et3SnOCH3 2) Br2 CH20H 3 ) Na2S203, KOH

Ph 92%

t

CHO Chem L e t t (1975) 145

ALDEHYDES FROM ALCOHOLS AND PHENOLS

SECTION 48

x

Br I

Pd( OAc ) ,,

73

82 %

JOC (1976)

41 1206

anodic o x i d a t i o n

OH

CH30H

dialdehyde

56%

acetals

40%

JACS (1975)

HO-( CH2)T-OFI

2) E t 3 N t

OHC-(CH2)5-CH0

JACS (1975)

R e l a t e d methods:

97 2546

97 2232

Ketones f r o m A l c o h o l s and Phenols ( S e c t i o n 168)

40%

74

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

Section 49

SECTION 49

Aldehydes from Aldehydes

-------- +

Me2CHCH0

Me2CHCH=N -t-Bu

1)

LDA, DME

tP

JOC (1974)

39

1) Me3CNH2, K2C03 ;

3) BzC1

76%

I

Me2

3102

Me

2 ) EtMgBr

Me2CHCH0

* PhCH2CCH0

2 ) PhCH2Br 3)

I

Bz-C-CHO

30%

I

Me Org Synth (1974)

54

46

Me -CHO

+

i 1 ) PhMgBr

___f

2 ) H30@

t - B u t y l - L - V a l ine -

II

0

CHO H

I

Ph 63% ee

JACS (1976)

98 7450

41 %

SECTION 49

ALDEHYDES FROM ALDEHYDES

75

92%

Chem B e r (1974)

107 367

1 ) BuLi,

92% Bu

2 ) BuBr S y n t h e s i s (1975) 720

T e t r L e t t (1976) 597

R e l a t e d methods: Aldehydes f r o m Ketones ( S e c t i o n 5 7 ) , Ketones f r o m Ketones ( S e c t i o n 1 7 7 ) . A l s o v i a : O l e f i n i c aldehydes ( S e c t i o n 341).

76

COMPENDIUM

S e c t i o n 50

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 51

Aldehydes from A l k y l s

OH

OH __KO-t-Bu 02'

90%

DMF iH0

CH3

Angew I n t Ed (1975)

S e c t i o n 51

14 356

Aldehydes f r o m Amides

n

n-C15H31CHO

l - C , 5H31CONMe2

71 %

Chem L e t t (1975) 875

"3

Ph-C-N

1 ) P0Cl3 2) Zn

t

Ph-CHO

JCS Chem Comrn (1976) 594

95%

SECTION 53

S e c t i o n 52

ALDEHYDES FROM ESTERS

77

Aldehydes f r o m Amines

No a d d i t i o n a l examples

S e c t i o n 53

Aldehydes from E s t e r s

NaA1H2(0CH2CH20CH3)2

88%

(SMEAH) CHZCHZCHO S y n t h e s i s (1976) 526

n

HA1 (N-NMe) P h-CH2CH2COOEt

PhCH2CH2CH0

76%

Chem L e t t (1975) 215

Bz

I

Cbz-NH-CH-COOMe

DIBALH

BZ

,

I

Cbz-NH-CHCHO

Chem Pharm B u l l (1975)

55%

2

3081

78

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 55

76-91%

Synthesis (1974) 808

Section 54

PhCH20CH3

Aldehydes from Ethers and Epoxides

uF6

___r

78%

PhCHO JACS (1976)

S e c t i o n 55

98 6717

Aldehydes from Halides

Li 1 ) MejSi!iSePh 2)

Ph(CH2)3CH0

H202

66%

T e t r L e t t (1976) 4223

NaH

a

70%

JCS Chem Comm (1974) 410

SECTION 55

ALDEHYDES FROM HALIDES

1 ) BuLi

+

2) n-C5H11Br

79

C5H1

CHO

-90%

3 ) H30@

JOC ( 1 9 7 5 ) $ 231 I -

Chem B e r ( 1 9 7 4 ) JOJ

Org Synth (1974)

RCH2Br

+

AgBF4

1 ) DMSO 2 ) EtgN

54

2295

42

RCHO

T e t r L e t t ( 1 9 7 4 ) 917

60-85%

80

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SMe

+

n-C5H111

I

LiCHSCNMe2

I1

-Hg++

MeOH

S

SECTION 5 5

n-C5H,1CH(OMe)2

70%

S y n t h e s i s ( 1 9 7 4 ) 705

( Me2N)2PON ( Me)CH2C=CH2

A

- 1)

BuLi OHC

Ic.

70%

CH2Ph

Comptes Rendus (1974)

A rX

279 609

ArCHO CHO

H2, CO, R3N

H e t ArX

H e t ArCHO

80-150"

J A C S (1974)

PBr

L iOP hSCuoyCH

60-90%

96

7761

( OE t )

CH ( O E t )

t

JOC (1976)

K2Cr04 h / B r

HMPT, c r o w n e t h e r

41 7 2 6

h

CHO

J C S Chem Comm (1976) 190

78%

81

ALDEHYDES FROM HALIDES

SECTION 55

JOC (1976) JOC (1976)

41 265 41 273

0

-NMezHCrO4

PhCHO

PhCH2Br

98%

T e t r L e t t (1976) 3985

70-95% (OMe, NO2, CN, COOR g r o u p s a r e i n c o m p a t i b l e ) Synth Comm (1974) 45

S

II

-NMe-

1 ) BuLi

+5

+

2 ) n-C Hl,Br 3 ) Hg , MeOH

,

n-C-H-.-b'.,

O , Me

dH O ' Me

S y n t h e s i s ( 1 9 7 4 ) 705

70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

82

S e c t i o n 56

SECTION 56

Aldehydes f r o m H y d r i d e s

CH2CT2 P

-70" X

6FjEtg0 2) Na2C03

VHO X

T e t r L e t t (1974) 3463

20-40%

90% HOAc

JCS P e r k i n I (1976) 540

SECTION 59

ALDEHYDES FROM OLEFINS

*F

Se02

COOMe

83

COOMe

glyme

Org React (1976)

S e c t i o n 57

41%

CHO

4 261

Aldehydes f r o m Ketones

No a d d i t i o n a l examples

S e c t i o n 58

n-BuCN

Aldehydes f r o m N i t r i l e s

@ 0 + Et30 BF4

S e c t i o n 59

1 ) Et3SiH

2) ~

3

0

n-BuCHO

71%

~

JCS Chem Comm (1974) 45

Aldehydes f r o m O l e f i n s

H2, CO, Et3N RhCl (CO)( PPh3)2

bCH

S y n t h Comm (1976)

82%

6

199

84

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

98 262

JACS (1976)

1) CO, PhH

/ c1

cpzr'o 2) H30@

O

'

JACS ( 1 9 7 5 )

Ph

---/ PhSH

C

H

O

97%

97 228

PhvSPh 1 ) NCS 2) C U ( I I ) ,

PhCH2CH0

60%

H20/acetone

JOC (1976)

S e c t i o n 60

SECTION 60

41 2769

Aldehydes f r o m M i s c e l l a n e o u s Compounds

1 ) BuLi 2 ) BzCl

[

:)-CH2CH2Ph N

Hg++ ---+

JOC (1975)

PhCH2CH2CH0

40 2021

56%

SECTION 60A

85

PROTECTION OF ALDEHYDES

S e c t i o n 60A

P r o t e c t i o n o f Aldehydes

JCS Chem Comrn (1975) 432

R-

") '0

Me

1,

R-

\

- HOCH2CH20H *

S

R-Ch0> \ 0

R-CH ( OMe ) T e t r L e t t (1975) 3267

Cl*

CH(SMe)2

S02C12, S i 0 2 H20, CH2C12

k

cl--@CHO

S y n t h e s i s (1976) 678

98%

86

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

& H

RCH2CN CHO

CHO

( R = CN

or C02Me) JOC (1976)

@A1

t

40 959

MeS\

PhNo a c i d c a t a l y s t r e q u i r e d .

R-CHO

48%

02N--@CH(0Bu)2

JOC (1975)

MeS-TMS

fi 2826

C1

n-butanol

PhCHO

SECTION 60A

Br2C( CH20H)2 TsOH, benzene, r f x .

90% H JACS (1975)

f

97

3229

R\(oy:l H

’

Zn/Ag

‘0

T e t r L e t t (1976) 4577

RCHO

>90%

SECTION 60A

87

PROTECTION OF ALDEHYDES

C HO Cu ( OAc ) H20/THF

100%

b

T e t r L e t t (1976) 3667

T1 ( N O 3 I 3

R = H, a l k y l , a r y l

R'CHO

4R

+ ROH + HC 0

%Me2

R-CHO

c

Chem Pharm B u l l (1976)

-

73-99%

41115

/OR R'CH

60-80%

O' R

L i e b i g s Ann Chem (1974) 690

R e l a t e d methods:

P r o t e c t i o n o f Ketones S e c t i o n 367

-

S e c t i o n 180A, Enol E t h e r s

-

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 5

PREPARATION

OF ALKYLS METHYLENES AND ARYLS

This c h a p t e r l i s t s the conversion o f f u n c t i o n a l groups i n t o Me, E t ..., CH2, Ph, e t c . Section 61

R-CZCH

Alkyls, Methylenes and Aryls from Acetylenes

FeCl 2-NaH i-

RCH2CH3

60-90%

R = alkyl , aryl

HC=CCH2CH2C?CH

Chem L e t t (1976) 581

MejSi CnCSi Mej CPCO( co 12 o c t a n e , rfx

SiMej

,

60%

SiMe JACS (1975) 97 5600 Angew I n t EdT1975) 88

14 712

ALKYLS FROM ALCOHOLS

SECTION 63

+

BrCH2CXH

-

CH2=CCH2ZnBr

I

Me

CH2C=CH2)2

k l

C (1975) 280 1389, 1473

Alkyls and Aryls from Carboxylic Acids

CH3(CH2),4COOH

Me3A1

a

CH3(CH2)14CMe3

91 %

Aust J Chem (1974)

Section 63

68%

Me

Comptes Rendus

Section 62

89

1665

Alkyls from Alcohols

Reactions i n which hydroxyl groups a r e replaced by alkyl, e . g . , ROH + RMe, a r e included in t h i s s e c t i o n . For t h e conversion ROH + RH s e e s e c t i o n 153 (Hydrides from Alcohols and Phenols)

R3COH

excess Me3A1

R3CCH3

f

100-200"

Aust J Chem (1974) 27 1639

PhCH20H

Ti C1 3- L i A1 H4 THF

+

PhCH2CH2Ph

JOC (1975)

78%

2687

90

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 64

A l k y l s from Aldehydes

S e c t i o n 64

JCS Chem Comm (1976) 757

Cp2TiC12

+

Na

--PhH

[Cp2TiI,-,

RCUO

JACS (1974)

1 ) PhLi

RCH3

96 5290

+

99%

2) L i , NH3

JOC (1976) 41 3465

ALKYLS, METHYLENES AND ARYLS FROM AMINES

SECTION 67

PhCHO

0

+

Zn 43%

BF3. E t 2O Tetrahedron (1975)

Review:

2 2785

"New A1 k y l a t i o n Methods Using Cyclopropyl Y l i d e s " Accts Chem Res (1974) 1 8 5

Related methods:

Section 65

Review:

A1 k y l s and Methylenes from Ketones ( S e c t i o n 72)

A l k y l s and A r y l s from Alky s and A r y l s

" P h o t o s u b s t i t u t i o n Reactions of Aromatic Compounds" Chem Rev (1975)

Section 66

A l k y l s , Methylenes and A r y l s from Amides

No a d d i t i o n a l examples

Section 67

A l k y l s , Methylenes -1s

No a d d i t i o n a l examples

91

from Amines

2 353

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

92

SECTION 68

Alkyls, Methylenes and A r y l s from Esters

S e c t i o n 68

66%

T e t r L e t t (1976) 2615

Cp2TiC12

+ Na

PhH

[.Cp2TiI,-,

RCOOR'

JACS (1974)

'$)

PhCO

NaCl, OMS0

96 5290

P h C O A

'

160"

RCH3

82%

Me

Me

T e t r L e t t (1975) 4389 Chem L e t t (1975) 1149

CH( OAcj2

AcOCHCMe2N02

I

I

Li-CMe2N02

80%

t

OMSO

NO2

NO2 T e t r L e t t (1975) 431

ALKYLS AND ARYLS FROM ETHERS

SECTION 69

93

DBU

%loo%

Br

S e c t i o n 69

T e t r L e t t (1976) 4435

A l k y l s and A r y l s f r o m E t h e r s

The c o n v e r s i o n ROR

+

RR' ( R ' = a l k y l , a r y l ) i s included i n t h i s section.

PhLi

100%

Et20 OMe

OMe

JACS (1975)

Me2C=CHCH20Et

n-C7H15MgC1

97

7383

Me2C=CHCH2C7H15

5% CuBr T e t r L e t t (1975) 3837

80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

94

Section 70

SECTION 70

A l k y l s and A r y l s from Halides

The replacement o f halogen by a l k y l o r a r y l groups i s included i n t h i s s e c t i o n . For t h e conversion RX RH (X-halo) see S e c t i o n 160 (Hydrides frorr; Halides and Sulfonates) -f

80%

T e t r L e t t (1976) 1161

-n-C5H1

Br

(K-B u ) *C uL i

.+

3-Methyloctane

94%

( a l k e n y l , a l k y n y l , a r y l , benzyl, a l l y l , and propargyl h a l i d e s a l s o work w e l l ) Org React (1975)

22

253

90%

JCS Chem Comm (1975) 561

SECTION 70

ALKYLS AN0 ARYLS FROM HALIDES

0-

Br

1 ) B u L i , -70"

95

75%

2) p C 7 H 1 5 B r , -50" S y n t h e s i s ( 1 9 7 5 ) 434

n = 3-5

T e t r L e t t ( 1 9 7 5 ) 2767

n-BuLi -100" 68%

JOC (1976)

Me SiCzCCH2N=CHPh 3

1 ) B u L i , THF 2 ) HC:CCH2Br

41 1184

Me3SiC=CCH-N=CHPh

I

CH2CcCH T e t r L e t t ( 1 9 7 5 ) 3337

62%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

96

db Br

SECTION 70

PhLi

Br

52%

I

Angew I n t Ed (1976)

B~

1 ) B u L i , THF, -95"

8,.

2) MeI, HMPA

15 762

86%

JACS (1975)

97 949

62%

T e t r L e t t (1974) 1207

Bu

RL i Et

I

Mn2+

85-90%

*

Et

R

J Organometal Chem (1976)

113 99

SECTION 70

EtMgBr

+

97

ALKYLS AND ARYLS FROM HALIDES

L i 2CuC1

C6H,10Ts

Et-C6H1

+

98%

-78" t o 25" Angew I n t Ed (1974)

PhCH2Li

+

-Q Et20

c) II I

t-Bu-CH-CHC1

\ 0/

+

86%

CH2Ph dH2Ph

JOC (1974)

-

13 82

n-BuLi -

-

3

1168

t-Bu-CH-CH-n-Bu -

\/ 0

-

T e t r L e t t (1974) 951

Ph 'CHC1

T i C1 3/LiA1 H4

+

Ph/

'"x:;

85%

Ph

S y n t h e s i s (1976) 607

t - BUN- Me

- - I

I40

1) LDA, THF, -80" 2 ) PhCH,Br L

+

-

t-BuNCH2CH2-Ph

1

NO

Chem Ber (1975)

95%

108 1293

98

COMPENDIUM

(PhS).#H2

+

OF

ORGANIC SYNTHETIC METHODS VOL 3

n-BuEr

NaNH2 THF, HMPA

'

(PhS)ZCBuz

SECTION 70

84%

S y n t h e s i s ( 1 9 7 5 ) 387

0

LDA

35%

THF -78" T e t r L e t t ( 1 9 7 4 ) 3963

8 .

0

Bu3BCH3 Li

+

CuCN ___r

682

PhCH2Bu

PhCH2Br

S y n t h e s i s (1976) 618

1 ) Mg, THF

57%

2) AgTf JOC (1976)

41 2882

SECTION 7 0

ALKYtS AND ARYLS FROM HALIDES

99

MgBr TlBr

2

benzene, THF, r f x

*

80%

CH3

CH3 Org S y n t h (1976)

EtC=CH 1

I

Bu

BuMgX

CU(1)

55 48

E tC=CHBu

7 3%

I

Bu Comptes Rendus (1974)

278

967

88%

MgBr

4 ) H30B T e t r L e t t (1976) 4697

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

100

1 ) Li, Et20 2) CUI

3) n-octyl-I, HMPA

c1

SECTION 70

2.90%

k

-n-oc tyl

Org Synth (1976) 55 103

55% Synthesis (1976) 40 NNHTs

It PhCCH2 I

PhCu, -60"

Br

-t-BuCO-C(t-Bu)Br2

Et20/THF

NNHTs

\I

PhC-CH2Ph

81%

JACS (1975)

+

Me2CuLi

97 7372

---H20

t-BuCOCH( Me) -

I

t-Bu

Comptes Rendus (1975) 280 217

90%

SECTION 70

ALKYLS AND ARYLS FROM HALIDES

/-------* H20 t-BuCHBrCOCHBr-t-Bu

+ Me2CuLi

101

t-B u ( Me ) CHCOCH2 I

85%

t-Bu(Me)CHCOCH(Me)t-Bu

80%

t-5u

Me I

T e t r a h e d r o n (1975)

3 1223,

1227

94% Tetrahedron (1976)

32

2281

45% T e t r L e t t (1974) 2935

T e t r L e t t ( 1 9 7 6 ) 3233, 3241, 3245

102

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

+

[PhSCuMeILi

THF

--+

&

JOC (1975)

BzBr

AgC104

benzene

SECTION 70

92694

Ph-CH2-Ph

52%

Coll Czech (1976)

41 1777

PhMgI

Ni(acac)p JOC (1976) 41 2252

70%

ALKYLS AND ARYLS FROM HALIDES

SECTION 70

1 ) Ph3P, Zn, DMF

( Ph3P ) pNi C 1

2) A r X

,

103

Ar-Ar

50-80%

T e t r L e t t (1975) 3375 JCS P e r k i n I (1975) 121 [ Pd( OAc)2 c a t a l y s t ]

JACS (1975) 97 3873 (intramolecular b i a r y l formation)

PhMgX

Mesityl B r

+

Ni(dpp)2Clp

Ph-mesi t y l

+

7 8%

Chem L e t t (1975) 133

H Ph

H

1 ) PdL4, PhH

2 ) MeLi, E t 2 0

Ph

J Organometal Chem (1975)

Me

88%

91 C39

PhI t

( Ph3P) ?Pd( Ph) I

51 %

t

J Organometal Chem (1976)

118 349

104

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

PhS02CHBr2

+

PhCH2C1

50% aq. NaOH

PhS02CBr2

I

TEBA

CH2Ph JOC (1975)

40

266

0" JACS (1974)

(allyl-SPh)'

+ allyl'C1

-

96 7355

biallyl

S y n t h e s i s (1974) 129 T e t r a h e d r o n (1974) 30 715

Review:

" O x i d a t i v e C o u p l i n g v i a Organocopper Compounds" Angew I n t Ed (1974) -(3 291

Review:

"The Ullmann S y n t h e s i s o f B i a r y l s " S y n t h e s i s (1974) 9

SECTION 70

75%

SECTION 71

Review:

i05

ALKYLS AN0 ARYLS FROM HYORIDES

"Activation o f Grignard Reagents by T r a n s i t i o n Metal Compounds" Tetrahedron (1975)

Section 71

31 2735

Alkyls and Aryls from Hydrides

This 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 R H -t RR' (R,R'=alkyl o r a r y l ) . For t h e r e a c t i o n C=CH + C=CR (R=alkyl o r a r y l ) s e e Section 209 ( O l e f i n s from O l e f i n s ) .

CH Ph I 2 1 ) BuLi 84%

2 ) PhCH2C1 Acta Chem Scand ( 1 9 7 4 )

Me

828

295

Me

LiA1H4

50%

diglyme JCS Perkin I (1976) 2380

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

106

SECTION 71

?Me

OMe 1 ) LDA, THF

60%

HMPA, -78" 2) CH2=C(Me)(CH2)2-I JACS (1975)

97 71 52

80-95% JOC (1975) 40 2021

hv

Ph2T10COCF3

Ph-Ph

+

benzene

95% JOC (1975)

PhCr( CO)j

1) t - B u L i 2) 12

2 PhHgOAc + Cu

+

40 2351

97%

Ph-C(CH3)3 JACS (1975) 2 1247

pyridi ne ._

PdC12, 115'C

+

Ph-Ph JOC (1976) 92661

86%

S

I1

PhCH2SCNMe2

-Me I

L DA

THF, -60"

I

S

II

PhCHMeS-C-NMe2

99%

MeSCH-CNMe2

90 %

THF

I

HMPA/THF

Ph

JACS (1975)

Review:

107

ALKYLS AND METHYLENES FROM KETONES

SECTION 72

2

1608

" A l k y l a t i o n and A r y l a t i o n o f U n s a t u r a t e d Compounds w i t h t h e A i d of T r a n s i t i o n Metal Complexes" Russ Chem Rev (1975)

S e c t i o n 72

44 552

A l k y l s and Methylenes f r o m Ketones

The c o n v e r s i o n s R2C0

+

RR, R2CH2. R2CHR',

etc. are l i s t e d i n t h i s section

1 ) E-BuLi

3) L i , E t 3 N T e t r L e t t (1976) 2643

65%

108

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 72

1 ) PhLi

91%

2 ) Li/NH3, NH,C1

1 ) MeLi PhhP'

2) L i , NH3,

NH4C1

JOC ( 1 9 7 5 )

40

JOC ( 1 9 7 6 )

41 1 4 9 4

271

t

Ph

Org Synth ( 1 9 7 6 )

55

JOC ( 1 9 7 5 ) 4 0 271 Synth Comm n 9 7 5 )

7

5 441

SECTION 72

ALKYLS AND METHYLENES FROM KETONES

A u s t J Chem ( 1 9 7 4 )

NHENHTs

~

6’

109

2 1655

92% 2 ) NaOAc

JOC (1975)

9 1834

-60%

JCS Chem Comm ( 1 9 7 5 ) 142

Ph-C-Et

Na@[ OBH C ( CH ) NP h 1 ’ CH2C1

+.

PhCH2Et

Chem Pharm B u l l ( 1 9 7 6 )

78%

3 1059

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

110

A

Ph

R,R'

=

-

Pd/C

Limonene

100%

JCS Chem Comm (1976) 757

E-alkyl

& ' :

PhCH2CH3

I

Me

SECTION 72

Tetr Lett (1976) 2643

P(red) + HI + I2

\

-+

0

ac 90%

Can J Chem (1974) 52 1229

00

I / II

Ph-C-C-CH3

1 ) (Me0)f

2) H2/cat.

,

PhCH2CCH3

JOC (1976) 41 2928

100%

SECTION 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

R e l a t e d methods:

A l k y l s f r o m Aldehydes ( S e c t i o n 64)

S e c t i o n 73

111

A l k v l s , Methylenes and A r y l s 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 74

A l k y l s , Methylenes and A r y l s f r o m 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 t y p e s a r e i n c l u d e d i n t h i s s e c t i o n : 1. 2. 3. 4.

5. 6.

Hydrogenation o f o l e f i n s (and a r y l s ) . Dehydrogenations t o f o r m a r y l s . A l k y l a t i o n s and a r y l a t i o n s of o l e f i n s . Conjugate r e d u c t i o n s o f c o n j u g a t e d aldehydes, ketones, a c i d s , e s t e r s and n i t r i l e s . Conjugate a1 k y l a t i o n s . Cyclopropana t i ons , i n c l u d i n g h a l o c y c l o p r o p a n a t i o n s

.

R

\=

R = a1 k y l , a r y l

FeC12-NaH

t

RCH2CH3

Chem L e t t (1976) 581

60-90%

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

112

1 ) LiA1H4, ZrC14 2) H20

J Organometal Chem (1976)

w

+

H2

* RhCl (PPh3)3 cat.

SECTION 74

,L90%

122 C25

N

100%

Org React (1976) 4 1

NH3(1), NaCl Me0

electrolysis

MeO Chem Ber (1976)

H2, NaBH4 NiC12

109 395

F

Z Naturforsch B (1975) 30 643

95%

SECTION 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

113

n

NH2

iHg +

60%

Pd, 140" T e t r L e t t ( 1 9 7 5 ) 4235

0

I

H20. 25"

cycl ohexane JACS ( 1 9 7 5 )

Ph

4 MeOH, Et3N

Ph

b

97 5249

PhCH2CH2Ph

S02NHNH2 T e t r a h e d r o n (1976)

32 2157

9D%

114

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

L i A1 H4/Ti C1 -pC6H1

r

SECTION 74

n-octane -

Tetr Lett (7976) 15

a e i r n i n o d i a c e t a t e + PdC12 C a t a l y s t f o r reduction o f conjugated d i o l e f i n s t o manoolefins a t 30" and 1 atm. H2. Chem Lett (1976) 165

f o r c a t a l y t i c hydrogenation of o l e f i n s . Rate i s 20-30 times g r e a t e r than t h a t f o r the f r e e c a t a l y s t .

Use o f

& +

H2

TiC1,

J Organometal Chem (1976)

1 atm. + n - a l l y l C ~ [ P ( O M e ) ~ ] ~-----+

25"

catalyst

Org React (1976)

120 49

0 31

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

SECTION 74

0

+

H2 ( 1 atm)

'0

a1 1y l Co [P ( OMe ) 3] 25"

96 4063

JACS (1974)

0

H2/Pt02 CF3COOH

Conc. HC1

70%

' JOC (1975)

40 2729

70%

r

Pt02, H2 JACS (1974)

96 2256

87:13 w i t h o u t HC1 13:87 w i t h 4N HC1

JOC (1975)

115

40 1191

116

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

Na E tOH

SECTION 74

ch

F

JOC (1975)

40

90%

2734

styrene, xylene Pd/C,

35%

rfx

Bull Soc C h i m Belges (1976)

+ Ph3COH

+

CF3COOH

-

T e t r L e t t (1974) 3217

3

1

SECTION 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

117

L i e b i g s Ann Chem (1974) 847

Fremy ' s

R

R

87-94%

30-74%

S y n t h e s i s (1974) 288

67%

T e t r L e t t (1976) 463

Ph2C=CH2

1 ) Na, THF t

2 ) PhCH2Br -78"

Ph2C-CH CH -CPh2

I

CH2Ph

2 1

CH2Ph

JCS P e r k i n I (1975) 1474

95%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

1i a

Q -

SECTION 74

hv

Org Synth (1976) 55 15

Review : "Cycl obutanes from Di meri za t i on of 01 ef i ns"

Synthesis (1974) 539

Ph

Ph

H2/Pd

CHO

basic ion exchange res i n

CHO

up to 100% selectivity

Bull Sac Chim France (1975) 2133

LiA1H4/CuI 0

r

xi: 0

Tetr Lett (1975) 4453

78%

SECTION 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

+ TiC13

"

20

119

86%

-----+

TH F

0 JOC (1974)

2 258

JACS (1974)

96 1625

80% Synthesis (1976) 596

Ph

CO/H20 Ph

83%

Rh4(CO) 12

Ph

(resin-supported) Chem L e t t (1975) 203

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

120

KHB ( EBu )

SECTION 7 4

9 82

THF

JOC (1975)

Me$

\

LiA1H4, C u I

*

40 146

Me3cL 99%

)-C/Me3 0

JOC (1976)

4

41 1939

2 LiA1H(OMe)3

84%

C u B r , THF

JOC ( 1 975)

a 3619

R u C l 2(PPh3)3/H2

40%

glucoside S 3 4 % ee T e t r L e t t ( 1 9 7 6 ) 4083

SECTION 74

ALKVLS, METHYLENES AND ARYLS FROM OLEFINS

Cornptes Rendus

PhCH=CHCOPh

K/NH3

C (1975) 281 877

98%

PhCH2CH2COPh

____+

Et20

Org React (1976)

0’

&

’

1

95%

0

H

Org React (1976)

Ph

23

Li/NH3 THF

121

3

Ph

them L e t t (1976) 695

1

122

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 3

SECTION 74

0YCHPh 4-ami n o b u t y r i c a c i d

56%

KOH, crown e t h e r

6

Synth Comm (1976)

NHCOPh

I i-PrCH=CCOOH

+

RhCl ( c h i r a l d i p h o s . ) cat.

113

H2

NHCOPh

I

i-PrCH2CHC02H optically active

Org React (1976)

41

* PhCH=C-COOH

I

$9

NHCOMe

I

PhCH2-CHCOOH r

I

NHCOMe

q:;;;

( S 93% ee)

1

=

C HMeNMe

*

T e t r L e t t (1976) 1133

..go%

SECTION 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

H2 HooC

NHC0CH3

[Rh(COD)L2]

*

PhCH2CHCOOH

>90% ee

I

@

123

NHCOCH3

Ph

JACS (1975)

97

2567

Br H2 b a c t e r i a ( C l o s t r i d i urn)

CH3CH2COOH

r

COOH

Angew I n t Ed (1975)

Ph

C02Et

14 106

C02Et

NaBH3CN

90%

C02E t

C02Et JOC (1976)

C6H,3CH=CHCOOMe

100%

LiBu-BH . l

t-BUOH

,-

41 3279

C6H1 3CH2CH2COOMe JOC (1975)

40

2846

92%

124

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

VOL 3

SECTION 74

76%

MxN

T e t r L e t t (1975) 1867

1

Mg, MeOH

7 7%

2 ) HCl

JOC (1975)

Ph

40

127

Ph NaBH4

NC

\

/ph

/

\

H - C A \ H

H

NC

100%

H

B u l l Chem SOC Japan (1976)

49

2643

CH3-(CH2)10-CH0

+ 0

II

0

Et3N t h i a z o l ium s a l t s

t-

0

II II CH3-( CH2)10-CCH2CH2CCH3

CH2=CH-C-CH3 Chem B e r (1976)

109 3426

76%

S E C T I O N 74

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

125

S y n t h e s i s (1974) 662

b

83%

JOC (1976)

41 3629

Me3A1/Ni(acac)2

68%

Et20

0

0 A u s t J Chem (1975)

1 ) Me2CuLi

86%

2) MeI, DME

JOC (1974)

28 801

39

275

126

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 74

Me3A1 , N i ( acac)2

JOC ( 1 974)

85%

39 3297

/ JACS (1974)

PhCH=CHN02

+

Me2CuLi

-

96 4334

PhCHMeCH2N02

54%

T e t r L e t t (1975) 3591

Review: " C a t a l y t i c T r a n s f e r Hydrogenation" Chem Rev (1974)

74

567

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

SECTION 74

+

TMSCHN2

A

127

72%

@TMS

JCS P e r k i n I (1974) 1440

T e t r L e t t (1974) 3329, 3333, 3327

1) L-BuOK, CHC13

2 ) L-BuOK,

Org Synth (1976)

Cp2Zr(C1)H

c1

e l 5%

DMSO

55

12

I-

J Organometal Chem (1976)

45%

108 C1

i28

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 74

1 ) CHC13, L-BuOK

1.35%

2) Na, NH3

Org Synth (1974)

3 11

+ L CH2CH=CH2

MeOH hv

Me

Me Helv Chim A c t a (1975)

PhCH=CHCOPh

70%

+

CH2N2

- A

58

178

Pd( OAc )

Ph

Et20

98% COPh

T e t r L e t t ( 1 9 7 5 ) 629 S y n t h e s i s (1975) 636

Br2CHCOOMe cu

COOMe

t

JACS (1976)

98

2676

71%

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

SECTION 74

6' 0

129

Met$ Me

C1

80%

LDA, -75" CH2C12

JACS (1975)

97

3830

PhHgCFBrCF3 155"

87%

'

W

C

F

3

J Organometal Chem (1975)

92 7

Et2Zn

84%

CHBr3, O2 JCS Chem Comm (1975) 364 B u l l Chem SOC Japan (1975)

93665

0

II

MeC- C=CH

II

Me

H2°

8 0

Et3NBzC1

Me Comptes Rendus (1974) 278 621 Synth Comm (1974) 4 3 4 1 S y n t h e s i s (1974) 736

130

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

JACS (1975)

97

SECTION 74

5956

C1 $-C02Na

57%

CHCl 3 , phase-transfer c a t a l y s t T e t r Lett (1976) 91

PhHgCClBrI

JOC (1975)

40 1620

SECTION 74

131

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

Ph3PbCC13

98%

+

125", octane

J Organometal Chem (1975)

90

I X

173

Me2 Me2C=CMe2

C1 3CSi F3

r

130"

98%

Me2

JCS P e r k i n I 1 (1975) 1051

CH=CH

CH=CHZ

CHC13, 50% NaOH phase t r a n s f e r c a t .

93% c1 T e t r L e t t (1975) 3013

132

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

+ CHC13 Ph

SECTION 74

50% NaOH

95%

TEBA, EtOH c1 S y n t h e s i s (1975) 323

90%

Z Chem (1975)

0

14

T i C14-LiA1 H4 +

CC14

79%

THF

Chem L e t t (1975) 711

Review:

" C y c l o p r o p a n a t i o n o f S i l y l Enol E t h e r s . A P o w e r f u l S y n t h e t i c T o o l " Pure & Appl Chem (1975)

Review:

"Chemistry o f Phosphorylcarbenes. Substrates"

43 317

Cyclopropanation o f Various

Angew I n t Ed (1975)

14 222

SECTION 75

ALKYLS, METHYLENES AND ARYLS FROM MISCELLANEOUS COMPOUNDS

133

"Two-Phase R e a c t i o n s i n t h e C h e m i s t r y o f Carbanions and Halocarbenes - A U s e f u l Tool i n Organic S y n t h e s i s "

Review:

Pure & Appl Chem (1975)

S e c t i o n 75

43 439

A l k y l s , Methylenes and A r y l s f r o m M i s c e l l a n e o u s Compounds

0

HFe(C0)4 PhhP'

DME

k

60%

PhCH2Ph

51 % JOC (1975)

3 2694

..

CH

JCS P e r k i n I (1976) 1257

Review:

"Novel Approaches t o A1 k y l a t i o n s " Pure & Appl Chem (1975)

43 563

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 6

PREPARATION

OF AMIDES

S e c t i o n 76

Amides from Acetylenes

R

RCrCR'

t

30-40% NCO

B u l l SOC Chim France (1974) 1949

0

Ph-C=C-MgBr

1 ) Me3SiNC0

2) H20

b

II

Ph-CiC-C-NH2

T e t r L e t t (1975) 981

134

48%

AMIDES FROM CARBOXYLIC A C I D S AND ACID HALIDES

SECTION 77

135

Amides f r o m 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

S e c t i o n 77

0 1 ) Ph,P(OTf)2

CH3COOH

2) PhNH2

b

II

CH3C-NHP h

80%

T e t r L e t t (1975) 277

PhCH2COOH

!-

PhCH2CNBu2

2 ) Bu2NH Chem L e t t (1975) 1163

Ph( CH2)nCOOH

+ HNR2

n

c1

10

Me

0

II Ph(CH2) N !, R2

betaine

= 0,1,2

R = Bu, Ph, Bz Chem L e t t (1976) 57

9 5%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

136

SECTION 77

0

PhCOOH

I1 63%

H

S y n t h e s i s (1975) 715

MeOCH2C02H

+

Me0 C1PO(OPh)2 Et3N

'

g ' l h

Ph-N=CHPh

0 Synth Comm (1976)

RCOOH

+

70%

N3PO(OPh)2

Et3N R'OH

6

435

RNHC02R' moderate t o h i g h y i e l d Tetrahedron (1974)

30

2151

0

/I

Ar-C-C1

+

ArCONH2

TMS2NOLi S y n t h e s i s (1975) 788

%50%

SECTION 77

PhCHCOCl

I

AMIDES FROM CARBOXYLIC A C I D S AND A C I D HALIDES

+ PhCH=NPh

-

OAc

137

Ph

Et3N

90%

OAc T e t r L e t t (1974) 2633 T e t r L e t t (1974) 3135 JDC (1974) 39 312

- AII

-CooH

CH3

CH3

CN3

EtOH 110"

CH3

0

T e t r L e t t (1976) 3089

Review:

"The Azide Method i n P e p t i d e Synthesis" S y n t h e s i s (1974) 549

Related methods:

Amides from Amines ( S e c t i o n 82)

NHCOEt

/I

0

80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

138

Section 78

ROH

SECTION 79

Amides from Alcohols

CD

0

+ Ph2CC1SbC16

0

R'CN

-----+

H20

----+

II

RNH-C-R'

40-86%

(used w i t h s t e r o i d a l a l c o h o l s )

JCS P e r k i n I (1974) 2101

3 0

ri

II

HNC- CH3

SOCl P

CH3CN

72%

JCS P e r k i n I (1976) 2205

Section 79

Amides from Aldehydes

RCHNOH

+

s i l i c a gel

Xylene, r f x

+

RCONH2

Tetrahedron (1974)

2 2899

61 -92%

139

AMIDES FROM AMIDES

SECTION 81

67%

JOC (1974)

S e c t i o n 80

2

3924

Amides from 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

S e c t i o n 81

Me2CHCONMe2

Amides from Amides 1 ) LDA, HMPA

Me2C-CONMe2 BU

Comptes Rendus (1974)

1 ) LDA

2)

86%

I

2) BuBr

278

1105

78%

BUI

JOC (1974)

2 2475

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

140

SECTION 81

66%

Can J Chem (1974)

52

3206

Et 85%

I

Me

Me

Can J Chem (1975)

53 1682

Ph

65%

Chem and Ind (1975) 745

RCONH2

NaOMe, MeOH, B r 2

-40 t o -15"

t

RNHCOCH3 (improved Hoffmann) S y n t h e s i s ( 1 974) 291

68-90%

141

AMIDES FROM AMIDES

SECTION 81

T FA JOC ( 1 9 7 6 )

0

II

1 ) C1 CH2SCH3, MeS03H

Ph-C-NH2

2 ) RaNi

41 725

0

II

83%

Ph-C-NHCH3

JCS Chem Comm ( 1 9 7 5 ) 3 2 0

I

I

CH2CH*P h

CH2CH2Ph

Chem P h a r m B u l l ( 1 9 7 6 )

Ph2C=0

I

Me Me

hv, O2

3 1992

66 0% 0%

c

I

Me Me JCS Chem Comm ( 1 9 7 6 ) 194

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

I42

SECTION 81

Me0 HO

COOEt

.COOEt

T1 (CF,COO)

Me0

23%

r

OH JACS (1975) 97 1239

k

Bu

NHCOCC13

+

(

bs H

CHO

CHO ____+

C1 3CCON

70%

Bu

JACS (1976) 98 2352

0

. txo DMSO I2

H

Synthesis (1975) 114

80%

AMIDES FROM AMINES

SECTION 82

Review:

143

" A l k e n y l a t i o n o f Imides and A c t i v a t e d Amides" S y n t h e s i s (1975) 685

Conjugate r e d u c t i o n s o f u n s a t u r a t e d amides a r e l i s t e d i n S e c t i o n 74 (Alkyls from Olefins). R e l a t e d methods: Amides f r o m H a l i d e s ( S e c t i o n 85)

S e c t i o n 82

Amides f r o m Amines

0 I

N y l o n 66

95%

f

TFAA

I

H

p 0

3

Angew I n t Ed (1976)

R

BuNH2

Ph-C-CF( CF3)2 TMED

777

0

II

BU-NH-C-Ph

Chem L e t t (1976) 673

100%

144

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

CHC13, NaOH

Et2NH

SECTION 82

E t2NCH0

phase-transfer cat.

78%

Z Chem (1974)

14 434

0

CN

AC20

-t

A

RCN

PhH s p e c i f i c f o r R=alkyl:

1 ACO-C-H I

+

RNH2

/I

RNH-C-CH3

----+

85-90%

CN

ArNH2, A r O H u n r e a c t i v e Synth Comm (1974)

Me

4 351

Me

I

I

80%

S y n t h e s i s (1975) 109

41 % BZ

BZ

JOC (1976)

fi 2780

SECTION 83

145

AMIDES FROM ESTERS

85% T e t r L e t t (1975) 2087

Me

\

N,

Ph

-

h- -hS

S

1

Me2NCPh

-60%

Ph

0

I n d i a n J Chem (1975)

dooH

13 35

1 ) LDA

2 ) Et20, O2

,N

2.50%

3) TsOH, THF

'CH2CH( OMe)2

'CH2CH( OMe)

T e t r L e t t (1976) 4613

R e l a t e d methods:

S e c t i o n 83

Amides f r o m 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 ( S e c t i o n 77) P r o t e c t i o n o f Amines ( S e c t i o n 105A)

Amides f r o m E s t e r s

No a d d i t i o n a l examples

146

COMPENDIUM

S e c t i o n 84

OF ORGANIC SYNTHETIC METHODS

SECTION 86

VOL 3

Amides from Ethers and Epoxides

No a d d i t i o n a l examples

Section 85

PhMgBr

Amides from Halides

1 ) TMSNCO 2 ) NH4C1, H20

PhCONH2

49%

T e t r L e t t (1975) 981

Section 86

Amides from Hydrides

1 ) Pb(OAcI4, CF3COOH

tD 2) H30 /CH3CN

78% NHCOCH3

Synthesis (1976) 32

SECTION 88 Section 8 7

AMIDES FROM NITRILES

147

Amides from Ketones

0

0

II

hu

Ph-C-NHL-BU

9 5%

JCS Perkin I (1976) 1511

Review:

"The Wi 1 1 gerodt Reaction"

0

It

Ar-C- ( CH2),H

S,

NH40H

Ar(CH2),CONH2 Synthesis (1975) 358

Section 88

Amides from Nitriles

RCN + PdC12 + H20

---+

RCONH2

A

Synthesis (1 974) 574

Ph-CZN

KOH

t-BuOH

0

II

Ph-C-NH2 JOC (1976) 41 3769

60-80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

148

Section 89

Amides from Olefins

No additional examples

Section 90

Amides from Miscellaneous Compounds

No additional examples

Section 90A Protection o f Amides

H2NCHCOOR'

I

Me

It

Ph2P-NHCHRCOOR'

R

R ' = Me, Bz

AcOH/HCOOH/H20 Tetr Lett (1976) 3623

SECTION 90A

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 7

PREPARATION

OF

AMINES

S e c t i o n 91

Amines f r o m A c e t y l e n e s

No a d d i t i o n a l examples

S e c t i o n 92

ArNH2

+

Amines 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

RCOOH

+ NaBH4

-

ArNHCH2R

JACS ( 1 974)

149

60-90%

96 7814

SECTION 94

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

I50

0

I1

1 ) benzene

D

/(CH2)8\

-40%

+

Org Synth (1974)

S e c t i o n 93

D-

Section 94 R2NH

+

3 88

Amines from Alcohols and Phenols

CH20H

1 ) NaH, DMF 2) PhJNMePhI

,@+

92%

BuMeNH, DMF T e t r L e t t (1975) 471

Amines from Aldehydes

R'CHO

+

NaHFe(C0)4

-

R2NCH2R'

Synthesis (1974) 733

60-80%

SECTION 94

151

AMINES FROM ALDEHYDES

+

LiA1H4

92%

_ I _ ) .

c1

Et

Et20

c1

S y n t h Comm ( 1 9 7 5 )

+

NH40Ac E t N 0 2 ___

3

269

N a ( MeOCH2CH20)2A1H2

JCS Chem Comm (1974) 307

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

152

c"

N=CH-CHMe2

Me0

1

1

+

+

SECTION 95

59%

I

-@MgBr

I

OMe Chem Ber

1975)

108 2827

Ph

P h- S-CH3

1) NaH, DMSO 2 ) PhCH=NPh

I

b

Ph

A

S y n t h e s i s (1976) 35

R e l a t e d methods:

S e c t i o n 95 No examples

Amines f r o m Ketones ( S e c t i o n 102)

Amines f r o m A l k y l s , Methylenes and A r y l s

47%

SECTION 96 Section 96

153

AFIINES FROM AMIDES Amines from Amides

0

NaBH4

PhCNHCH3 I1

AcOH

b

PhCH2NHCH3

82%

Tetr Lett (1976) 763

NHEt

NHCOCH3

I

I

same conditions

%loo%

Chem and I n d (1976) 322

3

Ph-C-N I;

TSNHCH2CH2-y-CH2CO2C6CI5 COCH3

1) P a 5

1

BH3.THF

2) H30$

3

Ph-CH2-N

b

2 ) NaBH4

+

TsNHCH CH -N-CH2COOH 2 1CH2CH3

JOC (1976) 41 149

90%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

154

SECTION 97

Me

HNCOCH3

Me+

Me Me T e t r L e t t (1976) 3217

S e c t i o n 97

Amines f r o m Amines

0

PhNH2

II

PhCOCH2S02C1 ')

Ph - C CH - SOZNP hB z

-

t

BzBr'

NaHC03

I

I

Bz

Zn, AcOH

HNPhBz

Tetrahedron (1975)

*60%

31 2517

SECTION 97

AMINES FROM AMINES

155

S y n t h e s i s (1975) 596

1) LiAlH4

88%

2 ) EtOAc

I

H

Et

S y n t h e s i s (1975) 607

KOH, B z B r

DMSO, 25" I

H

OR

I

85%

BZ

NaH, HMPA BzCl

Org Synth (1974)

54 58,

60

COMPENDIUM OF ORGANIC SYNTHETIC

156

METHODS VOL 3

SECTION 97

CO, KHFe(C0)4

-1 00%

).

HCHO

I

d

Me B u l l Chem

BzNH2

Ph2POC1

Ph2PONHBz

Et3N

1 ) NaH 2) Me1

s

SOC Japan (1976) 49 1378

8

0

BzNH2Me OTs

56%

3 ) MeOH, TsOH

T e t r L e t t (1976) 4005

R-NH2

R

NaHC03, Me1 MeOH

8 0

75-96%

RNMe31

= amino a c i d

Also works w i t h secondary amines. Can J Chem (1976)

2 3310

AMINES FROM AMINES

SECTION 97

157

1 ) Me02C( CH2)@r

90%

P

1

2)

H

a

I

( CH2) 5COOMe

98 2344

JACS (1976)

Me Ph-NH

I

+

CH3CH2COOH

I

NaBH4

Ph-N

___).

65%

I

Me

CH,CH~CH~

JOC (1975)

CH3COOH NaBH4

3

3453

Go

%-

68%

I

it Synthesis (1975) 650

{

>N-Me

P h-0-C-C1

84-89%

KHC03, r f x

morphine, codeine JOC (1975)

40 1850

158

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

F-

q L o

I

Q1 t

SECTION 97

75%

N"2

S y n t h e s i s (1975) 710

1 ) C1 $CH20COC1 CH3NR2

2 ) Zn/HOAc b-

R2NH

>70%

(proceeds i n 75% w i t h morphine) T e t r L e t t (1974) 1325

&

HBr

83%

I

CH2CH=CMe2 S y n t h e s i s (1975) 440

SECTION 97

AMINES FROM AMINES

159

NHCH P h Pd. ( PPh3),

complex

*

AcO

JACS ( 1 9 7 6 )

Ph3P

+

CCI4

+

CH3CH(OH)CH2NHCH2Ph

+

98 8 5 1 6

Et3N

YH3

R

=

a 1 k y l , Bz

- '"b

80%

I

Chem B e r ( 1 9 7 4 )

RNHCH2CH2CHOH

67%

/

Et3N

Ph3PBr2 Et3N

r

/N R

107 5

'7,

Synthesis (1974) 894

44-65%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

160

+

COOMe

Ph

I

COOMe

+

Me2S=CHCOPh

Ph

SECTION 99

Ph %OPh

I

Ph

COOMe

85%

COOMe

JOC (1975) 40 2990

Review:

"Umpolung o f Amine Reactivity"

Angew Int Ed (1975) 14 15

Section 98

Amines from Esters

No additional examples

Section 99

Ph

Amines from Epoxides

A

0I I

BzN-P( OEt)

r

Ph

Tetr Lett (1976) 4003

58%

SECTION 100

S e c t i o n 100

161

AMINES FROM HALIDES

Amines f r o m H a l i d e s

Monatshefte (1976)

ArI

+

(Me3Si)2NCu

-MeOH

107 401

30-60%

ArNH2

JCS Chem Comm (1974) 256

60 %

Et

Comptes Rendus

C

(1975)

281 47

162

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

+

PhLi

HMPA

THF

-30"

PhLi

[.complex]

PhCH2NHMe

__+

JOC ( 1 9 7 4 )

NH2NH2

+ CHC13

+

KOH

ether

18-crown-6

.b

SECTION 100

75%

9 3042

40%

CH2N2

Tetr L e t t ( 1 9 7 4 ) 2 9 8 3

R R'

I I

HCZC-C=C-CH2C1

1 ) NHMe2 2)

NaOH

R\ b

/

R'

55-60%

Me

Comptes Rendus ( 1 9 7 4 )

278 801

I

Me

Org Synth (1974) 54 93

SECTION 102

AMINES FROM KETONES

163

1 ) Me1

0

II

2) E t I

Me2NNHCCH3

3) O ' H,

H20

'

H2N-NMeEt

2.80%

JOC USSR (1975)

S e c t i o n 101

11 56

Amines from Hydrides

NH - t - 8 ~

Se ( N -t-Bu)

62%

JACS (1976)

S e c t i o n 102

98 269

Amines from Ketones

NOH

H LiA1H4

54%

H2(0CH2CH20CH3)2

Can J Chem (1975)

53 3227

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

164

SECTION 102

55%

T e t r L e t t ( 1 9 7 6 ) 1175

N-OR

H T e t r L e t t (1975) 3263

Ph-C-CH2Ph

II

NOH

1) (i---Bu)MgBr

,,VPh H

Chem Pharm

Bull (1976) 24 1083

49%

SECTION 103

AMINES FROM NITRILES

Ph-C-CH2Me

I1

iu' \

PhMgBr

o

NMe31

0

+

Ph

165

kfMe

80%

H

T e t r L e t t (1975) 355

R e l a t e d methods:

S e c t i o n 103

Amines f r o m Aldehydes ( S e c t i o n 94)

Amines from N i t r i l e s

NaBH3(0COCF3)

PhCH2CN

P hCH2CH2NH2

TH F

70%

T e t r L e t t (1976) 2875

Me0 MeO-@Br

Me0

FH-CN

____+ B2H6

MeO&

OH

CHCH2NH2

t

OH Does n o t hydrogenolyze h a l i d e s . JCS P e r k i n I (1974) 1015

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

166

S e c t i o n 104

SECTION 1 0 4

Amines f r o m O l e f i n s

CYNHPh

1 ) L i , THF

KB r

87% S y n t h e s i s (1975) 116

R3B

or R2BH

+

MesS03NH2

-

RNH2

24-50%

S y n t h e s i s ( 1 9 7 4 ) 196

0

II

1 ) (Et0)2PNBr2,

BF3.Et20

2 ) NaHS03 3) L i A I H q

Angew I n t E d (1976)

302

SECTION 105

AMINES FROM MISCELLANEOUS COMPOUNDS

Angew I n t Ed (1974)

&ph \

N3

PhH

~

167

13 279

+ph\

0

H

92%

0

JOC (1974) 39, 775

S e c t i o n 105

Me &NO2

Amines f r o m M i s c e l l a n e o u s Compounds

-

RuCl 2( PPh3)3

Me &NO2

H2

T e t r L e t t (1975) 2163

91%

168

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

JOC (1975)

SECTION 105

40 519

Me

0

97%

i-PrOH

0

Synthesis ( 1 9 7 6 ) 528

H2NNH2

jH2 99%

FeC13/activated C CH3 Chem Lett ( 1 9 7 5 ) 259

SECTION 105

AMINES FROM MISCELLANEOUS COMPOUNDS

FNo2 Pd-C

NH2

169

95%

cyclohexene

ethanol, r f x

NO2

NO2

JCS P e r k i n I (1975) 1300

PhN02

1 ) (NH4)2S 2)

HF

p-F - P hNH

L

30%

JOC (1974)

2

1758

pyridine/Hp

90%

Pd( acac)2 Chem and I n d (1975) 1057

Ph-N3

vc1 q

L

+

PhNH2

70%

H20/THF Synthesis (1976) 815

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

170

Ph

"2

N3

SECTION 105

Ph

Lindlar catalyst

93%

+

NH2 Synthesis (1975) 590

TiC13

Me

4 0

NH2

83%

MeOH/H20

Me

NH2

Synthesis (1975) 335

& I

NO

H2, Ra-Ni

MeOH, 200"

95%

'

I

H

Synthesis (1976) 548

SECTION 105

AMINES FROM MISCELLANEOUS COMPOUNDS

171

1) BuLi, BzBr

I

:

NO

BZ

BZ

2) (repeat)

+Bz

:rliele

NO

I

’

H

76% S y n t h e s i s ( 1 9 7 6 ) 540

Ph

OH

NCH2NCH2Et

I

H

F

I

EtCHN2

NO Chem P h a r m B u l l ( 1 9 7 6 )

/

65%

24 369

N=N - NMePh

72%

Bull Chem SOC Japan (1975)

48 2397

172

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

Section 105A

SECTION 105A

P r o t e c t i o n of Amines

“ B i c ” p r o t e c t i n g group f o r amine f u n c t i o n s i n p e p t i d e synthesis. Removed by Et3N/DMF f o l l o w e d by h y d r o l y s i s o r by hydrogenolysis.

T e t r L e t t (1975) 4625

A p h o t o l a b i l e p r o t e c t i n g group f o r h i s t i d i n e :

PCH2-d

NHBOC

I

CH2CHCOOH

I

NHBoC

hv

/=-(cH2CHCooH HN

dN

NO2 JACS (1975)

3 440

Use o f t h e “Dobz” amine-protecting group t o vary s o l u b i l i t y p r o p e r t i e s o f r e a c t a n t s and products i n p e p t i d e synthesis.

T e t r L e t t (1975) 4629

PROTECTION OF AMINES

SECTION 105A

173

The introduction of tertiary amino substituents into urethane-type amino protecting groups increases their acid-stability and provides a functional group which can be used to alter solubility characteristics.

0

II

example:

/

JCS Chem Comm (1975) 939

CH3-CH-COOH

I

NH2

0-CN3

CH3CH-COOH H*/Pd liq. NH3

I

HN-L-Boc JACS (1974)

96 4978

Cleavage of t-Boc, Z(OMe), and NPS protecting groups by CF3S03H in polypeptide synthesis. JCS Chem Comm (1974) 107

Use o f the 2-(tripheny1phosphonio)ethoxycarbonyl group as an amino protective function in peptide chemistry. Stable to acids, removed with base. Chem Ber (1976) 109 2670

174

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

RCH- COO^ I

SECTION 105A

02N RCH-COOH

+

$3

Stable to DCC

I cyclohex. JOC (1974) 39 3351

Cleavage o f Na-benzaloxycarbonyl from methionine via H2/Pd in 1 iquid NH3.

1

PhCH20-C-R, PhCH20R, PhCH20C(0)-R are cleaved. 0

II

t-BuO-C-R, t-BuO-R, etc. are

not cleaved. Tetr Lett (1974) 3259

Me3SiC104 cleaves the t-Butoxycarbonyl (BOC) group selectively in the presence o f benzyloxycarbonyl (Z) groups and t-butyl esters. Angew Int Ed (1975) 14 818

175

PROTECTION OF AMINES

SECTION 105A

R

I

H2N-CH-COOH.Et3N t

H20/Dioxane

CN

80-90%

F

I

T e t r L e t t (1975) 4393

Bz

Bz

I

H2N-CH-COOH

Me2PhS iH

N i , THF

F

I

Me2PhSi-NH-CH-COOSiMe2Ph

75%

T e t r L e t t (1975) 3207

i

Ph-NHC-OCH2CH2C1

Co ( I ) p h t ha1 ocyan ine

83%

PhNH2

Angew I n t Ed (1976)

681

Use o f C 1 ~ O C H 2 0 - C ( C F 3 ) 2 t o b l o c k i m i d a z o l e i n h i s t i d i n e

I

/N\ U 1 ) s t a b l e t o s a p o n i f i c a t i o n and H2 2 ) removed by m i l d H+

3) d e r i v a t i v e s s o l u b l e in o r g a n i c s o l v e n t s T e t r L e t t (1974) 2637

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

176

SECTION 105A

as NH2 or OH p r o t e c t i n g group i n n u c l e o t i d e s and

Use o f CH2-

-L

n u c l e o s i d e s . Removed b y Ac20 f o l l o w e d b y NH3/MeOH.

0 JOC (1974)

2

1250

Me0 Sugar

-

NH2 +

Me0 OMe

NO2 JOC (1974)

Use o f PhCH2- t o p r o t e c t b a s i c N i n a l k a l o i d s .

39

192

Removed by pPrSLi/HMPA a t 0"

Synth Comm (1974)

Me

I

5

H

.

HC1 50-70%

t

I

R

R

R = alkyl

183

JOC (1975)

40 1353

SECTION 105A

PROTECTION OF AMINES

177

x]

NH2

Eq

kN

0

1 ) Na2S 2 ) DCC Y

3) NH2NHCH3

0'

R-NH-NPS

JACS (1975)

0/

97 5582

2.100%

R-NH2

NPS = o - n i t r o p h e n y l s u l f e n y l H e l v Chim Acta (1976)

59 855

S y n t h e s i s (1976) 40

Review:

" S t a b i l i t y o f Side Chain P r o t e c t i n g Groups i n Solid-Phase P e p t i de S y n t h e s i s " I s r a e l J Chem (1974)

12 79

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 8

S e c t i o n 106

PREPARATION OF ESTERS

Esters from Acetylenes

Ph

Ph CO, PdC12

HgCl

LiC12, MeOH

\

JOC (1975)

S e c t i o n 107

COOMe

9 3237

E s t e r s f r o m 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

The f o l l o w i n g t y p e s o f r e a c t i o n s a r e f o u n d i n t h i s s e c t i o n : 1. E s t e r s f r o m 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 f r o m h y d r o x y a c i d s .

3.

E s t e r s f r o m c a r b o x l i c a c i d s and h a l i d e s , s u l f a t e s , and m i s c e l l a n e o u s compounds.

178

100%

SECTION 107

ESTERS FROM CARBOXYLIC ACIDS AND ACID HALIDES

-

179

Use of "graphite bisulfate" t o catalyze esterification RCOOH + R'OH

RCOOR'

Fast, high yield; excess R'OH is not required. 3" alcohols undergo elimination.

JACS (1974) 96 8113

Use of BF3.Et20.ROH to effect esterification o f carboxylic acids Synth Comm (1974) 4 167

1 ) Ph3P(Off)p

M e O 4 C O O H OMe

R-COOH

R

=

BzOH, DCC BuOH,

pyridine

N-protected amino acid

2 ) EtOH

+

Me0 OMe

Tetr Lett (1975) 277

*

%85%

R-COOBZ

Z Naturforsch

(1976) 31 1157

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

180

SECTION 107

c-0 -tBu

o+c.cl 1) TlS-L-Bu 2) L-BuOH

Hg(OCOCF3

l2 J A C S (1975)

Ph-COOH

100%

t

97 3515

P

P hCOOCH3

2) MeOH, E t 3 N

S y n t h e s i s (1975) 456

Chem L e t t (1975) 1045

93%

SECTION 107

ESTERS FROM CARBOXYLIC A C I D S AND A C I D HALIDES

b e t a ine

ROH

n

181

= 1, 2

R = Ph, a l k y l , cinnamyl, e t c .

Chem L e t t (1976) 13

HO-(CH~)~COOH

n

= 5,7,10,11,14 Chem L e t t (1976) 49

HO-(CH2)15-COOH

+

-

Ph3P

P

0

! 7 L

(A$> t-Bu

Y

1

83%

5

T e t r L e t t (1976) 3409

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

182

SECTION 107

-

2,2 ' d i pyr idy 1 di sul f i de

Ph3P

c

OR

OR

JACS (1975)

91 653,

I

OR

92%

654

0

HO- ( CH2), 7-COOH

BF3*Et20

II 78%

polystyrene Synthesis (1976) 738

HO- ( CH2)

+

-COOH

Ph3P

63%

___j

EtOOC-N=N-COOEt Tetr Lett (1976) 2455

ESTERS FROM CARBOXYLIC A C I D S AND A C I D HALIDES

SECTION 107

JACS (1974)

96

183

5614

F u r t h e r examples o f t h e r e a c t i o n RCOOH + ROH-tRCOOR a r e i n c l u d e d i n S e c t i o n 108 ( E s t e r s f r o m A l c o h o l s and Phenols) and S e c t i o n 10A ( P r o t e c t i o n o f Carboxyl i c A c i d s ) .

+

R-COOK

MeCN BZCl

RCOOBZ

------+

TMEDA

R = hindered a l k y l

Comptes Rend

0 0

Ph

‘COOH

C

(1976)

Ph

Resin-NMe,OH

L -

%80%

i- P r B r

283 483

i\

59%

YC-O -I-

0 S y n t h e s i s (1975) 723

00

Ph-COOH

+ CH2C12

B u ~ NOH

88%

>

T e t r L e t t (1975) 2303

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

184

SECTION 107

0

Synth Comm (1976) 6 89

RCOY

-t

0

PhCH2N (Me)2Ph

a

RC02CH2Ph

65-80%

Synthesis (1974) 727

JCS Chem Corn (1975) 412

Me0 Me0

CH2COOH

+ HCHO

-=MeoHC 1

mo

Me0

Org Synth (1976) 55 45

56%

SECTION 107

ESTERS FROM CARBOXYLIC A C I D S AND A C I D HALIDES

185

1 ) BuLi

high y i e l d JDC (1974)

2 2783

0

S y n t h e s i s ( 1974) 81 1

0 RCOOH +

R’SH

NCPO(OEt)2 E t 3 N in DMF

t

I1

RC-SR‘

JOC (1974)

70-95%

3

3302

186

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

S e c t i o n 108

Esters from Alcohols and Phenols

n-C - 16H33OTHP

TFAA

89%

n-C H OCOCF3 16 33

----+

CH2C1

Synth Comm (1976)

MeOH

SECTION 108

Ph-C-CF( CF3)2

5

21

89%

Me-0-C-Ph

P

TME D Chem L e t t (1976) 673

Ph

Ph

\

0

II

ph\

Me$-C- C 1

’

O+/Tl

Ph N-N’

o 7 5%

00v0!!-CMe3

Bu

Bu JOC (1976)

2 165

F u r t h e r examples o f t h e r e a c t i o n ROH R’COOR 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 from C a r b o x y l i c Acids and Acid H a l i d e s ) and Section 45A ( P r o t e c t i o n o f Alcohols and Phenols). -f

BuONa

+ CO

Se BuOH, THF

*

80%

(BuO)~CO B u l l Chem SOC Japan (1975)

48 108

187

ESTERS FROM ALCOHOLS AND PHENOLS

SECTION 108

j

CH3C( OEt)

85%

PhOH

OH

Angew I n t Ed (1975)

El-

N-COOEt

14 103

@

L-

CHzO-!-Ott

(MeZNl3P

T e t r a h e d r o n (1975)

31 1411

Ac5H1

Ag2C03/Cel it e

HOH2C

CD20H

10%

90% Tetrahedron (1975)

2 171

T e t r L e t t (1976) 3305

71%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

188

S e c t i o n 109

SECTION 109

E s t e r s from Aldehydes

ROSnBu3 t

R'CHO

0

NBS CC14

II

R'-C-OR

+

R = alkyl R ' = a l k y l , Ph

JACS (1976)

1 . 10% H2S04

+

2. Ag2C03-cel it e xylene, r f x

98 1629

phb

71%

0

JOC (1975) 40 892

PhCH( OCH2CH=CH2)2

L3

Ph-C-OCH2CH=CH2 Synth Comm (1975)

Related methods:

Esters from Ketones ( S e c t i o n 117)

72%

5

213

SECTION 112

Section 110

ESTERS FROM AMINES

189

E s t e r s from Alkyls, Methylenes and Aryls

No examples of t h e r e a c t i o n R R + RCOOR' or R'COOR ( R , R ' = a l k y l , a r y l , e t c . ) occur i n the l i t e r a t u r e . For the r e a c t i o n RH + RCOOR' o r R'COOR see S e c t i o n 116 ( E s t e r s from Hyrides).

Section 111

E s t e r s from Amides

Chem Ber (1975)

RCONHR'

RC02Rf

t

108 48

R'N=SPh2

Rf = PhC(CF,)*

JACS ( 1 9 7 5 )

Section 112

Esters from Amines

No a d d i t i o n a l information

97

6137

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 3

190

S e c t i o n 113

SECTION 113

Esters from Esters

100%

JOC (1974)

39 2323

MeOCCHCCOOLi

I

Li

71% 2)

H30 @

JOC (1976)

1)

94065

LOA

COOMe COOMe

JACS (1976)

1204

SECTION 113

ESTERS FROM ESTERS

1 ) L-Selectride

C6H, 3CH=CHCOOMe

2) PhCH2Br

+

191

C7H, 5CH( CH2Ph)C02Me

JOC (1975)

Et3SiCH2COOMe

1 ) (Me3Si)*NNa 2)

*

40

2846

Et3SiCHMeC02Me

86%

Me1 J Gen Chem USSR (1975)

E t C C l 2C00-1-Pr

1) L i , THF 2)

Me1

3

45

78

E t C C l ( Me)CO2-L-Pr

J Organometal Chem (1975)

MeSCH2CH=CHCOOMe

50%

1 ) LDA, THF

85%

102 129

MeSCH=CHCHMeCOOMe

2) Mel, HMPA

92%

T e t r L e t t (1975) 405

EtOOCCH2N=C(SMe)2 + J-BuOK

+ Me1

-

EtOOC-CH-N=C(SMe)2

I

Me Angew Chem I n t Ed (1975)

14 424

70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

192

Me C1CC 00H

1 ) L i t TMP

+

Me2C=CH( CH2)2CzCCOOMe

THF, HMPA

SECTION 113

50%

2) Me2C=CHCH2i3r

3 ) Me1

JOC ( 1 9 7 5 )

40

269

70%

JOC (1976)

CH2(COOMe)2

+

U t

5 2039

Bz-CH( COOMe)2

Bz-Br L i e b i g s A n n Chem ( 1 9 7 6 ) 348

84%

SECTION 113

ESTERS FROM ESTERS

193

Ph P=C=C=O 3

78% Me Angew I n t Ed (1976)

v

3)

cop electrolysis MeOH

0

0

+

EtO-C-H

NaOMe

115

92%

0

JOC (1974)

II

3

+

O2

Se

cat.

3

2486

0

II

EtO-C-OMe

T e t r L e t t (1974) 804

PhCHO

+

0

0s iMe3

II w

I1

N2

I

PhCHC-COOEt

II

OEt

N2

JOC (1976)

41 3335

86%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

194

SECTION 114

Conjugate r e d u c t i o n s o f u n s a t u r a t e d e s t e r s a r e l i s t e d i n S e c t i o n 74 (Alkyls from O l e f i n s )

Section 114

E s t e r s from Ethers

Se02

85%

0

Org R e a c t ( 1 9 7 6 ) Q, 261

' *I

R R CC02Li t

Li

Aust J Chem (1974)

0

CH3COOH

Ph

-----+

C <'H2Li

2)

H30@

JOC (1974) 3 2783

27

2205

ESTERS FROM HALIDES

SECTION 115

FeCl 3-Ac20

R-OR'

195

ROAc + R'OAc

(ally1 ethers not rearranged or isomerized) JOC (1974) 3 3728

Section 115

ArX

Pd",

Esters from Halides

CO

MeOH, Et2NH

c

ArCOOMe

Phl + CO + EtOH + Et3N

Bull Chem SOC Japan (1975) 2 2075 JOC (1975) 9 532

+

Pd(0) cat MeNH2

---+

PhCOOEt

90%

PhCONHMe

JOC (1974) 3 3318 JOC (1974) 3 3327

40-60%

JOC (1974) 3 1761

196

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

RBr + Hg(N03)2

-

RON02

SECTION 115

60- 100%

28 cases

Tetrahedron ( 1 9 7 4 ) 30 2467

RBr + Hg(0Ac)2 t AcOH

-

ROAc

88-98%

15 cases Tetrahedron (1974) 3 2467

RX

t

RX

+ Ag02CR'

Na02CR'

HMPA

TH F

R02CR'

Comparison o f these methods.

R02CR' JOC (1974)

2 3721

1 ) LDA

Oxazol ine

OMe

u

92%, 72% ee

JOC (1975) 40 1186

SECTION 116

ESTERS FROM HYDRIDES

1 ) L i I C A , THF

H02CCH2CODEt

2 ) PhCH2Cl

t

PhCH2CH2COOEt

JOC (1975)

R e l a t e d methods:

S e c t i o n 116

I97

7 5%

40 2556

C a r b o x y l i c A c i d s f r o m H a l i d e s ( S e c t i o n 25)

Esters from 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' or R'COOR ( R = a l k y l , a l l y l , a r y l , e t c . ) and A r H + Ar-X-COOR ( X = a l k y l c h a i n )

COOMe

2.90%

T e t r L e t t (1975) 3973

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

198

b i s - (2,2 ' - b i p y r i d i n e ) s i 1v e r ( II ) - p e r o x y d i sulfate OMe

@ Y O A c

HOAc

1 ) Pb(OAc)4, CF3COOH

+ @

8

(1975)

CHCOOMe

I

S y n t h e s i s (1976) 32

S e c t i o n 117

29 629

87%

2) E t h y l a c e t o a c e t a t e

COOEt

Also via:

183% (based on Ag)

OMe A c t a Chem Scand

Adaman t a ne

SECTION 117

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

E s t e r s f r o m Ketones

T e t r L e t t (1975) 1841

S E C T I O N 117

199

ESTERS FROM KETONES

R'

seve ra 1

COOMe

"x""

COOMe

R'

R

>=O R'

Rv . R'

COOMe

RxcH2c COOMe

R'

JACS (1975)

97

2218, 2224

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

200

SECTION 117

S y n t h e s i s (1975) 404

Ph-CEC-0

+

0 51 %

h

May b e p r o t o n a t e d , d e c a r b o x y l a t e d , o r further alkylated. Angew Int Ed (1975)

14 765 OAc

Zn, HC1

+ Ac20, Et20

H e l v Chim A c t a (1976)

40%

2 962

SECTION 119

ESTERS FROM

OLEFINS

201

1 ) O3 (-60") 45%

-

0

2 ) NaBH4

Me

d

Me

JOC ( 1 9 7 5 )

40 2970

A l s o 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 27

S e c t i o n 118

Esters from N i t r i l e s

72%

5

2)

H30@ S y n t h e s i s (1976) 238

S e c t i o n 119

E s t e r s from O l e f i n s

1 ) 1 / 3 BH3

BuCH=CH2

2 ) Hq(OAc)2

BuCH2CH20Ac

3 ) 12

JOC (1974)

39

834

86%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

202

SECTION 119

.AH RC-0-L-Bu

NzCHCOO-_t-Bu Rh(O-CO-_t-Bu)z

Me

-?.-CgH11

Synthesis (1976) 600

Angew I n t Ed (1975) 14 716

R

=

H, l o , Z " , 3' alkyl

Chem Pharm Bull (1976) 24 538

JACS (1974) 96 7977 JOC (1974) s 3 4 5 6 A l s o v i a Alcohols, Section 44

89%

PROTECTION OF ESTERS

SECTION 120A

S e c t i o n 120

E s t e r s f r o m M i s c e l l a n e o u s Compounds

No a d d i t i o n a l examples

S e c t i o n 120A

Protection o f Esters

No a d d i t i o n a l examples

203

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 9

S e c t i o n 121

PREPARATION OF ETHERS AND EPOXIDES

Ethers and Epoxides from Acetylenes

No examples

S e c t i o n 122

Ethers and Epoxides from Carboxylic

No a d d i t i o n a l examples

Section 123

ROH

+

Ethers and Epoxides from Alcohols and Phenols

CH31

+

NaH

-

ROCH3

Synthesis (1974) 434 204

high y i e l d s

SECTION 123

ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS

205

90%

Br EtOH JCS P e r k i n I (1975) 461

RBr

t

+ R'OH

HgC104

ROR'

____+

74-98%

23 cases T e t r a h e d r o n (1974)

ArOH

+ RX

phase t r a n s f e r cat.

t

+ Me2S04 + NaOAc

2467

&I

1379

ArOR

T e t r a h e d r o n (1974)

Polyphenol

&I

acetone------+

d i oxane

m e t h y l a t i o n o f most a c i d i c OH group

I n d i a n J Chem (1974)

12 893

CH30H, Ph3P PhOH

N-COOEt

PhOCH3

II

N- COOEt

Chem and I n d (1975) 281

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

206

SECTION 123

0

( Me2N)3P-O-CH2-t-Bu

+

66%

Angew I n t Ed (1975)

14 370

H20, NaOH/CH2C12,

Me I

HO

S t e r o i d s (1976)

R e l a t e d methods:

481

P r o t e c t i o n o f Alcohols and Phenols ( S e c t i o n 45A)

T e t r L e t t (1975) 2731

SECTION 123

ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS

207

64%

JACS (1975)

97

465

moderate t o h i g h y i e l d s JACS (1974)

96 4604

JCS P e r k i n I (1974) 1637

208

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 124

4 molecular weight % l o JOC (1975)

S e c t i o n 124

f

R'OH

1515

Ethers and Epoxides from Aldehydes

-

OR'

RCHO

3

___+

I

'ZH6 TH F

R-C-OR'

I

RCH20R'

H

Can J Chem (1974)

52

60-90% 888

AcOH

JOC

PhCHO t

TsCH2C1

50% aq. NaOH TEBA

(1974)

39 2740

/O\

60%

Ph JOC (1975)

40 266

SECTION 128

ETHERS AND EPOXIDES FROM ESTERS

209

00

PhCHO

Me3SI, NaoH

(-)-N,N-dimethylephedrinium bromide

77%

ph

(R)-67% e e JACS (1975)

Section 125

97 1626

Ethers and Epoxides from Alkyls, Methylenes and Aryls

No examples o f the p r e p a r a t i o n o f ethers and epoxides by replacement o f a l k y l , methylene and a r y l groups occur in the l i t e r a t u r e . F o r t h e conversion of RH + R O R ' ( R , R ' = a l k y l ) s e e S e c t i o n 131 ( E t h e r s from Hydrides)

Section 126

Ethers and Epoxides from Amides

No a d d i t i o n a l examples

Section 127

Ethers and Epoxides from Amines

No a d d i t i o n a l examples

Section 128

Ethers and Epoxides from E s t e r s

No a d d i t i o n a l examples

210

COMPENDIUM OF

S e c t i o n 129

ORGANIC SYNTHETIC METHODS VOL 3

SECTION 130

E t h e r s and E p o x i d e s . f r o m E t h e r s and Epoxides

(YOH

CH30H a1 umi na

66%

O ' CH3

T e t r L e t t (1975) 3597

0 0

79%

Chem L e t t (1975) 1051

S e c t i o n 130

BzCl

+ Bu-OH

Ethers from Halides

50% NaOH Bu4N@ H S O ~ Q

'

Bu-0-BZ

T e t r L e t t (1975) 3251

92%

MeOCH2CH20H

21 1

ETHERS FROM HALIDES

SECTION 130

1) TlOEt

2) BzBr, MeCN

+

MeOCH2CH20Bz

81 %

Angew l n t Ed ( 1975)

JOC (1976)

2 762

41 732

75%

JOC (1976)

41 1184

21 2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

S e c t i o n 131

SECTION 132

Ethers from Hydrides

No a d d i t i o n a l examples

S e c t i o n 132

E t h e r s and Epoxides f r o m Ketones

OCH3

1 ) TsNHNH2

7 7%

2) NaBH4, MeOH JOC (1976)

fl 1755

PhCHO Angew I n t Ed (1975)

14 350,

700

ETHERS AND EPOXIDES FROM KETONES

SECTION 1 3 2

NTs

1 ) NaH, DMSO

II

Ph-S-CH2CH3

213

54%

2 ) PhCOCH3

p

Me

h

A

M

e

S y n t h e s i s (1976) 35

Ph2C0

50% a q . NaOH

+

TEBA

TsCH2C1

+

phA Ph

Ts

JOC ( 1 9 7 5 )

0 1 R CHBrC-S-1-Bu

il

40 266

0

NaH

JOC ( 1 9 7 5 )

40 31 73

90%

21 4

SECTION 133

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

8

Me

PhS-CH-SePh

1 ) BuLi

I

Me

3) AgBF4, Me1

4) J-BuOK, DMSO

Tetr Lett (1975) 1617

2) CH31

3) HO'

Angew Int Ed (1976)

Section 133

Ethers and Epoxides from Nitriles

No additional examples

15 437

2.35%

SECTION 134

Section 134

ETHERS AND EPOXIDES FROM OLEFINS

21 5

Ethers and Epoxides from O l e f i n s

65%

JCS Perkin I (1976) 605

-

$*+ COOH

\cx.

)4+& 50-90%

0//C-OOH

Use of polymer supported p e r a c i d s t o epoxidize o l e f i n s . JCS Chem Comm (1974) 1009

T e t r Lett (1976) 207

216

Ph

\

Ph

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

/Me

hv,

I\

02

c , -c

benzi1

Me

Ph

SECTION 1 3 4

M ,e

80%

M 'e

JACS ( 1 9 7 6 )

3 4193

0

I/

PhC-N=C=O

JCS Chem Comrn ( 1 9 7 4 ) 7 1 1

OCOMe

{a

{j.f~"..

{D

NBS

1 ) B r 2 . H20 2) MeCOOH

2)'

OMe

r

%70%

JACS ( 1 9 7 5 )

L i TMP

E tOCH2C1

97

3185

r

T e t r L e t t (1976) 3779

55%

SECTION 135

MeCH=CHMe +

21 7

EPOXIDES FROM MISCELLANEOUS COMPOUNDS

PhSCH2C1

50% NaOH phase t r a n s f e r

79%

Me

Me

T e t r L e t t (1975) 4247

Review:

"Metal Ketenides i n t h e C a t a l y t i c E p o x i d a t i o n o f O l e f i n s " Chem and I n d (1975) 154

S e c t i o n 135

Epoxides from M i s c e l l a n e o u s Compounds

No a d d i t i o n a l examples

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 10

PREPARATION

OF HALIDES AND SULFONATES

H a l i d e s and S u l f o n a t e s f r o m A c e t y l e n e s

S e c t i o n 136

CH3,

MoCl

CH3-C5C-CH2CH3

3 8%.

c1/c=c\ JACS (1975)

S e c t i o n 137

PhCOCl

+

/CH2'"3

____+

c1

97 1599

H a l i d e s from Acid H a l i d e s

SF4

95"

PhCF3

95%

Org React (1974)

21 8

2

1

SECTION 138

S e c t i o n 138

219

HALIDES AND SULFONATES FROM ALCOHOLS

H a l i d e s and S u l f o n a t e s f r o m A l c o h o l s

Ph3P g e r a n y l -OH

b

sao%

g e r a n y l -C1

cc1

MeLi, TsCl

or -

L i C l , HMPA/Et20

t

Org Synth (1974)

PhCH20H

t

54 63,

PhCH2C1

CC14 JCS Chem Comm (1975) 622

PC13,DMF n-BuOH

ZnCl

t

n-BuC1 -

S y n t h e s i s (1976) 398

68

88%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

220

PBr3 OH

SECTION 138

+ T 6 7%

4"C, 1-2 days

Br

97% r e t e n t i o n o f c o n f i g u r a t i o n JOC (1976)

6

fi 1071

@dPPh2 c1

92%

cc1 JOC (1975)

o\ OH

I

9 1669

0

II

~-COO-~-BU I 0

JACS (1975)

R-OH

R

t

PC1,3

= 3" a l k y l

CHCl CaC03

c1

I

97 2281

R-C1 retention o f configuration Aust J Chern (1976)

2

133

SECTION 138

HALIDES AND SULFONATES FROM ALCOHOLS

221

76% Can J Chem (1975)

n-Hexyl-OH

+ aq. HC1

phase t r a n s f e r

cat.

53 3620

n-Hexyl C1

>go%

-.

S y n t h e s i s (1974) 37

00

[Me2NCHBr]

Br

r

MeCN

OH

Br

1.80% y i e l d 1.75% ee ( r e t e n t i o n ) JCS P e r k i n I (1976) 754

BzOH

Et2NSF3

CH2Cl

+

100%

BzF

Et2NSF3

88%

diglyme

JOC (1975) 3 574

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 3

222

C6F5CH20H

f

SFq

85'

C6F5CH2F

F.

80%

Org React (1974)

ROH

+ SeF,

-

SECTION 139

31

RF

40-90%

' JACS

Q

(1974)

96 925

0

MeS02NMeEt2FS03

98% JACS (1975)

S e c t i o n 139

PhCHO

+ SF4

97

2566

Halides and Sulfonates from Aldehydes

160"

PhCHF2

81%

Org React (1974)

Section 140

11

Halides and Sulfonates from Alkyls

No a d d i t i o n a l examples

For t h e conversion RH+RHal s e e Section 146 (Halides from Hydrides)

SECTION 144

HALIDES FROM ETHERS

S e c t i o n 141

H a l i d e s and S u l f o n a t e s f r o m Amides

223

No a d d i t i o n a l examples

S e c t i o n 142

H a l i d e s f r o m Amines

qNH2 QfBr H2Q Cu2Br2/HBr NaN02

70-90%

10-15" S y n t h e s i s (1974) 292

S e c t i o n 143

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

No a d d i t i o n a l examples

S e c t i o n 144

Halides from Ethers

Br

3- Ph P B r 2 alkyl

H---

I

c-c,

a1 k y l

JOC (1976)

fi 3279

Br

I

85% a1 k y l

224

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

S e c t i o n 145

RX

+

KF

SECTION 145

H a l i d e s f r o m H a l i d e s and S u l f o n a t e s

phase-transfer c a t a l y s t

good y i e l d

RF

b

120-160" S y n t h e s i s (1974) 428

0

H Br - 16 33 n-C

resin-NMe3

F

0 t

n-C H F - 16 33

7 7%

S y n t h e s i s (1976) 472

CH2F

CH20Ms

I c=o

I

c=o

H e l v Chim Acta (1976)

y 3 Hex- CHO Ms (R)

KC 1 phase-transfer c a t a l y s t

P

Hex-CHC1

(S) 89% ee

S y n t h e s i s (1975) 430

59

1027

74%

SECTION 145

HALIDES FROM HALIDES AND SULFONATES

R-C1

225

R-Br

t

NaBr, E t B r R = 1" a l k y l

B u l l Chem SOC J a p a n ( 1 9 7 6 )

PPh3Br2 C-C16H330THP

'

87%

"-C16H33Br S y n t h Comm ( 1 9 7 6 )

I

6 21

Br

OTs

Angew I n t Ed ( 1 9 7 5 )

t-BuC1 -

+

FeC13

9 1989

+

I

-

14 824

t-BuI -

T e t r L e t t ( 1 9 7 4 ) 2691

95%

226

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 145

0 I

80%

Bull SOC Chim France (1976) 169

Me2CEt

I c1

NaI, CS2

ZnCl

.

96%

I

JCS Perkin I (1976) 416

56%

JOC (1976) 41 24

P hS02CH2CH20H

1 ) BuLi

2) Hexyl Br

r

PhS02CHCH20H

I

Hex Bull SOC Chim France (1976) 519

%loo%

SECTION 146

227

HALIDES FROM HYDRIDES

cso2

CH2Ph

1 ) BuLi, THF-hexane 2 ) PhCH2C1

65%

I

I

Me

tie JOC (1975)

HCBr3

1 ) LDA, THF-Et20-110"

___

+

2 ) BUI

S e c t i o n 146

40 1342

BuCBrj

90%

B u l l SOC Chim France (1975) 1797

Halides from Hydrides

JACS (1976)

98

3036

228

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

F2/He

SECTION 146

perfluoro

3.5%

JACS (1975) 97 513

70%

Synthesis (1976) 33

F XeF2

OMe

CH2C1

71%

t

0Me 10:1:8 o:m:p

JOC (1975) 3 807

HALIDES FROM HYDRIDES

SECTION 146

229

E x p e r i e n t i a (1976)

Br

15 417

Br

2.85%

cF3

cF3

Org Synth (1976)

55 20

Br

S y n t h e s i s (1976) 621

230

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 146

OH

OH

TlOAc, I2

-50%

HOAC

R R = H. a l k y l ,

R

aryl JCS P e r k i n I (1976) 1161

(Me-@$-T10COCF3

12

2

86 %

HCCl

JOC (1975) 2351

6

1) T1 (OCOCF,)

2)

80%

KI CH3

I

CH3

Org Synth (1976)

E 1ec t rogene r a t e d Iodine ( I ) JACS (1976)

55

Ph-I

98 1515

70

91%

SECTION 148

0 :: T1(OCOCF3)2

OMe

OMe

PI

OMe

+

SeF4

-

N02

60-90%

RCF2R'

110

96 925

r\c

0

/

@

( Et0)2P-CBr2Li

67% S y n t h e s i s (1976) 197

No examples

98%

H a l i d e s f r o m Ketones

JACS (1974)

S e c t i o n 148

@

40 3441

JOC (1975)

R-C-R'

i

" ~ ~ ' *

Tl(OCOCF3)3

S e c t i o n 147

231

HALIDES AND SULFONATES FROM NITRILES

H a l i d e s and S u l f o n a t e s from N i t r i l e s

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

232

S e c t i o n 149

SECTION 149

Halides from Olefins

F o r a l l y l i c h a l o g e n a t i o n see S e c t i o n 146 ( H a l i d e s f r o m H y d r i d e s ) F o r 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 )

Ph ti

I I . I I XeF2

/"="\

Ph

Ph-C-C-

CF3COOH

F

CH3

JOC (1976)

MoCl

CH3

9 5%

F

5 4002

t

Q--"'

66%

%1

JACS (1975)

97 1599

5 8%

S t e r o i d s (1975)

5 619

SECTION 149

233

HALIDES FROM OLEFINS

1 ) L i A 1 H 4 , ZrC14 *

0 -

rB-

2) Br2

92%

J Organometal Chem (1976) 122 C25

CpZr(H)Cl

+

-

7 &rB-

96%

JACS (1974) 96 8115

'Tb-)

Et

I

Me-CH \

1 2 , CH30H

NaOCH3

2

H2C=CH(CH2)8COOMe

1) B2H6, THF

*

CH3CHCH2CH3

I I

49%

R c o n f i g . , 84% ee JACS (1976) 98 1290

2) 12, NaOCH3

b

I-CH2( CH2) &OOMe

Synthesis (1976) 1 1 4

68%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

234

S e c t i o n 150

Me-C-SeR

I H

SECTION 150

H a l i d e s f r o m M i s c e l l a n e o u s Compounds

Br

2

Me- C- Br

84%

I

H T e t r L e t t (1976) 2647

Me.+-CHCOOH

I I

SH NH2

CF30F

Me2C-CHCOOH f

l i q u i d HF

I I

F

JOC (1976)

Review:

fl 3107

"Advances i n t h e S y n t h e s i s and I n v e s t i g a t i o n o f Organof l u o r i n e Compounds" Russ Chem Rev (1975)

Review:

94%

NH2

44

339

"Some Recent Developments i n O r g a n i c C h l o r i n e C h e m i s t r y " Chem and I n d (1975) 249

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 11

PREPARATION OF HYDRlDES

T h i s c h a p t e r l i s t s h y d r o g e n o l y s i s 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 a r e r e p l a c e d by hydrogen, e.g. RCH2X -* RCH2-H o r R-H

S e c t i o n 151

Hydrides from Acetylenes

No examples o f t h e r e a c t i o n RCzCR

S e c t i o n 152

-c

RH o c c u r i n t h e l i t e r a t u r e

ljydrides from Carboxylic Acids

No a d d i t i o n a l examples

S e c t i o n 153

H y d r i d e s 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 p h e n o l s , ROH + RH

235

236

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 153

83%

Ooklady Chem (1974) 219 888

0 OH

I1 I

Ph-C-CH-Ph

red P

Ph-C-CH2Ph

12

90%

Synthesis (1975) 161

rph

pyri dine

S

2.65%

JCS Perkin I (1975) 1574

Ph- C-OH

I

CH3

1 ) Na, NH3/THF

2) NH4C1

CH3

r

I I

Ph-C-H

CH3 JOC (1975) 40 3151

9 5%

SECTION 153

Ph

HYDRIDES FROM ALCOHOLS AND PHENOLS

tt-

237

BF3 1-NapPhMeSi H*

OH

86% ph+

H

T e t r L e t t (1976) 2955

phL/

45%

CH20H

CH3 Chem Ber (1976)

HO

n-C8H170H

J4 + RNCNR

CUCl

7

TiC14 LiA1H4

+

109 1586

a}

Chem Pharm B u l l (1976)

!-‘aH1

7-’-‘\

-

fiNR H2 Pd,C NHR

65%

3 825

octane

Chem Ber (1974) 107 1353 Chem Ber (1974) 907

90%

COMPEf4DIUM OF ORGANIC SYNTHETIC METHODS VOL 3

2 38

PhOH

-

0

SECTION 154

0

PhOS03 NHR2Ph

I 1) KOH

PhH

94%

2) RaNi JCS P e r k i n I (1975) 169

Meo),N-cHo U

OH

phenyl t e t r a z o l e

2 ) H5-chloro-11 p , Pd/C N-CHO

k

2.50%

/

’0

Rec Trav Chim (1976)

95 43

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 the conversion RCHO

-+

RMe e t c . see Section 64 ( A l k y l s from Aldehydes)

HYDRIDES FROM AMINES

SECTION 157

S e c t i o n 155

2 39

H y d r i d e s 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

S e c t i o n 156

H y d r i d e s f r o m Amides

No a d d i t i o n a l examples

S e c t i o n 157

H y d r i d e s f r o m Amines

T h i s s e c t i o n l i s t s examples o f t h e c o n v e r s i o n R N H p RH

ArCH2NH2

+ 2) NaBH4 3) 200"

+

ArCH3

Ph

Ph

0 T e t r L e t t (1976) 2689

50%

240

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

3 ) HMPA;

powdered glass JOC (1974)

ClOH21NHZ

-

S

1317

NaBH c1 OH2 1NTs2

4

HMPA

*

JOC (1975) S e c t i o n 158

SECTION 158

ClOH22

91%

2018

Hydrides from E s t e r s

T h i s s e c t i o n l i s t s e x a m l e s o f t h e r e a c t i o n s RCOOR'+RH and RCOOR'+R'H.

A1203 I(CH2)6C02Et

&co2R

K2C03, butanone, r f x

R = H, Me, E t T e t r L e t t (1976) 2707

80-90%

HYDRIDES FROM ETHERS

SECTION 159

241

0

0

*

II

CH3(CH ) CHCCH3 COOEt

/I

0-

CH3( CH2)6CH2CCH3

x y l e ne

same c o n d i t i o n s

b

C

H

3

CH3

COOEt Synth Comm (1975)

5

341

JCS Chem Comm (1975) 439

S e c t i o n 159

H y d r i d e s from E t h e r s

No a d d i t i o n a l examples

97%

98%

24 2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

S e c t i o n 160

SECTION 160

H y d r i d e s from H a l i d e s and S u l f o n a t e s

T h i s s e c t i o n l i s t s t h e r e d u c t i o n of h a l i d e s and s u l f o n a t e s R X

2vc1

+

RH

96%

H20/THF S y n t h e s i s (1976) 807

R-CC1 2-CO0 -

R-C-CO

%80%

R = alkyl R ' = a l k y l , acyl

S y n t h e s i s (1975) 533

Ph ( CH2) $r

Bu3SnCl ( 0 . 1 e q u i v ) NaBH4, hv

*

PhCH2CH2CH3

JOC (1975)

88%

40 2554

SECTION 160

243

HYORIDES FROM HALIDES AND SULFONATES

JOC (1975)

40 1966

1 ) Li-NH3 Me0

2 ) PhCOONa

Me

’

Me0O

M

JOC (1975)

3 2238

JOC (1976)

41 1393

45%

e

( n-Cp)2TiC12/Mg 87%

Br

H JDC (1975)

40 31 59

244

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 160

60%

Br

PhCH2Br + K ( ~ - B u ) ~ B H +

Tetr Lett (1975) 2257

-

CuI

PhCH3


JCS Chem Comm (1974) 762

Bu

Bu

81%

JACS (1975) 91 2558

D

D

60%

20%

JOC (1974) 39 2300

PhCC1=CH2

245

HYDRIDES FROM HALIDES AND SULFONATES

SECTION 160

t-BuLi

Et20

71 %

PhCHZCH-t-Bu

Tetr Lett (1975) 2935

7 X or

i-PrMgCl

7 H

1 % MnC12

or

Ar-H

Ar-X

J Organometal Chem (1976)

a

+

NaH

TH F

87%

rfx

OMe

OMe

JOC (1974)

113 107

2 1425

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

246

SECTION 162

OTs 80%

JOC (1976)

41 3064

Na(Hg) , MeOH COzMe

Na2HP04

C02Me

S02Ph T e t r L e t t (1976) 3477

T e t r L e t t (1976) 3325

Section 161

Hydrides f r o m H y d r i d e s

No a d d i t i o n a l examples

SECTION 165

S e c t i o n 162

HYDRIDES

FROM MISCELLANEOUS COMPOUNDS

H y d r i d e s f r o m Ketones

No a d d i t i o n a l examples

F o r t h e c o n v e r s i o n R2C0

+

R2CH2 o r R2CHR' see S e c t i o n 72 ( A l k y l s and

Methylenes f r o m Ketones)

S e c t i o n 163

Hydrides 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 164

Hydrides from O l e f i n s

No a d d i t i o n a l examples

S e c t i o n 165

H y d r i d e s f r o m M i s c e l l a n e o u s Compounds

No a d d i t i o n a l examples

247

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 12

PREPARATION

OF KETONES

S e c t i o n 166

Ketones from Acetylenes

4 0

/I

CH2CCH3

0’

JACS (1975)

1 ) LiC:CH R3B

2 ) HC1

+

RCOMe

97 5249

70-90%

3) NaOH, H202

JACS ( 1 975) 97 501 7 T e t r L e t t (1975) 3327 (more f u n c t i o n a l i z e d alkynes)

KETONES FROM CARBOXYLIC A C I D S AN0 A C I D HALIDES

SECTION 167

1 ) TFA, NaOCOCF3

HCEC-CH~

I

2)

CH20S02CF3

+

%35%

H20 Org Synth (1974)

54 84

a

PhCH20CaCH

249

75%

T e t r L e t t (1975) 3275

OMe

0

II

Ph-CZC-C-CH

CH30H 3

-

NaCN

I I

Ph-C-CH2COCH3 OMe JOC (1976)

Section 167

41 3765

Ketones from C a r b o x y l i c Acids and A c i d Halides

T e t r L e t t (1975) 4611

86%

250

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 167

NaHC03

44%

4

21 ) LDA MeSSMe

'

____r

-

+COOH

NCS

COOH JACS (1975)

97 3528

H2C = CHCMe2COMe

55%

CH2-CHCMe2COOH

Me2C=CHCH2COMe

50%

T e t r L e t t ( 1 9 7 5 ) 3179

EtC02Li

+

PhLi

Et20

+

EtCOPh

82%

rfx 24 h r s .

JOC (1975)

40 1770

BuL i

76%

-100" JOC (1975)

40

2394

SECTION 167

KETONES FROM CARBOXYLIC A C I D S AND ACID HALIDES

n-C4HgC0 ( CH2) 4COC1

(J-BuOCuBu-J)L

i +

n-C4H9CO(CH2)4CO-t-Bu

Org React (1975)

JOC (1974)

+ PhCOCl

&(cN

22

251

73%

253

3 3241

0 JCS P e r k i n I (1975) 129, 142

0

Q@

Ph4BLi

+

PhCOCl

-

!

A

Ph

Ph

JCS Chem Comm (1975) 738

80%

252

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

LiBBzBu3

+

PhCOCl

Ji

THF/Hexane +

Bz

JOC (1975)

C:k

SECTION 167

88%

Ph

3

1676

CH2CH2MgBr

0 t

r

II

CH3( CH2)5CCH2CH2CH0

2 ) H20, o x a l i c a c i d

CH 3( CH2) &OC1

JOC ( 1 9 7 6 )

82%

41 560

0

II

-n-Hep t-MgBr

1 ) Mn12 2 ) J-BuCOC1

n-Hept A

r

-

B- u

80%

T e t r L e t t (1976) 3155

0

/I

Ph-C-C1

0

PhS[Me3C]CuL i TH F

*

I1

85%

Me3C-C-Ph

Org S y n t h (1976)

CH2=CH2 +

PhCOCl

L3RhH( CO)

P

55

PhCOEt

JACS (1974)

96 4721

122

50-80%

SECTION 167

KETONES FROM CARBOXYLIC ACIDS AND ACID HALIDES

+ RhC1(CO)(PPh3)2 + PhCOCl

BuLi

-

90%

PhCOBu

JACS (1975)

97

5448

5me2 II

1 ) BuLi, THF

(MeC0)2C=SMe2

253

55%

PhCOCH2COCCOMe

2) PhCOCl

JCS Chem Comm (1975) 289

a

4

F0

/

P

h

1 ) 1-PrMgX r

2 ) hydrolysis

PhCOOH

i-PrCOPh quant.

Gazz Chiw I t a l (1975)

907

0

I1

Ph-C-Br t

86%

Chem L e t t (1975) 951

PhCOCl

+ PhH

CrC13.5 DMSO r

80%

PhCOPh

J Gen Chem USSR (1974)

44 2316

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

2 54

S e c t i o n 168

SECTION 168

Ketones from Alcohols and Phenols

Cr03 Ph /'\Ph

HMPT

100%

t

Ph

Ph

Synthesis (1976) 394

C5H5NHCr03C1 ( p y r i d i nium chlorochromate)

97%

T e t r L e t t (1975) 2647

7 7%

JACS (1976)

RCHR'

I

OH

+ Na2Cr207

OMS0

+ conc. H2S04

98 6737

RCR'

JOC (1974)

80-90%

2 3304

SECTION 168

KETONES FROM ALCOHOLS AND PHENOLS

255

1 ) Et3SnOCH3

OH

I

Ph-CHCH3

2 ) Br2

3) Na2S203, KOH

k

PhCOCH3

78%

Chem L e t t (1975) 145

80%

Chem L e t t (1975) 691

6

NaOCl

89%

tetrabutylammonium bisulfate T e t r L e t t (1976) 1641

6

DMSO TFAA

65%

Et3N JOC (1976)

2 957

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

256

SECTION

168

DMSO TFAA

JOC ( 1 9 7 6 )

on

I

Ph-CH-Ph

It

41 3329

0

PhI(OCCF3)2 +

I1

Ph-C-Ph

65% S y n t h e s i s ( 1 9 7 5 ) 445

JCS P e r k i n I ( 1 9 7 5 ) 1614

6

MCPBA

JOC ( 1 9 7 5 )

40 1860

KETONES FROM ALCOHOLS AND PHENOLS

SECTION 168

257

n

OH CH-CH3

98%

THF, HC1 T e t r L e t t (1975) 4115

0 OSnBu3

NBS

JACS (1976)

-

RCH-R'

C'P

I

pyri d i ne

OH

85%

cc1

98 1629

RCR'

2">1 O

6 I

T e t r L e t t (1974) 3059

C1 3CCH0 2'3 T e t r L e t t (1976) 3499

71 %

2 58

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

1;

1 ) TMSCl 2 ) Ph3CBF4

92%

3) H20

fi 1479

JOC ( 1 9 7 6 )

OH NO @' BF4 Me

SECTION 168

CH2C1

dMe 78%

~

Me

S y n t h e s i s ( 1 9 7 6 ) 609

74%

JOC ( 1 9 7 6 )

fi 889

JOC ( 1 9 7 6 )

41 3030

SECTION 168

259

KETONES FROM ALCOHOLS AND PHENOLS

MeCN Ph-CHOH

b

Bu4NBF4

PhCOCH3

82%

electrolysis Et

IPh-C-OH I

0

II

same

conditions

___t

t-Bu

82%

Ph-C-Et

JACS ( 1 9 7 5 )

97 4012

a&:-q:: CHCl Mn02

OH

0

Indian J Chem ( 1 9 7 6 )

Tetr Lett ( 1 9 7 6 ) 4597

146 1 4 3

260

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

b

SECTION 168

(5

OH

CH20H

CH20H

-

Br2/HMPT

*

93%

Synthesis (1976) 811

97% T e t r L e t t (1975) 273

H?5H6r* 0 B u L i , THF

9

-78 t o 0"

JACS

70-90%

0

1974)

96 6510

b

0 0

It I1

hv 'gH6

Synth Comm (1976)

6

281

100%

SECTION 169

I R-C-R' I

KETONES FROM ALDEHYDES

261

0

+

II

hv

O2

Rose Bengal

H

JACS (1974)

RuHCl( PPh3)3

R 1CH=CH-CH-R 2

I

96 585

R ~ C HCH C-R'

211

110"

OH

high y i e l d

R-C-R'

-----+

80- 90%

0

T e t r L e t t (1974) 4133

CuTf, PhH

EtZC-CH( SPh)2

t

I

L DA

OH

EtCOCH-SPh

Et JACS (1975)

R e l a t e d methods:

S e c t i o n 169

88%

I

97 4749

Aldehydes f r o m A l c o h o l s and Phenols ( S e c t i o n 48)

Ketones f r o m Aldehydes

JOC (1975)

40 231

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

262

ArCHO

1 ) KCN, Et2NH

43%

2) B a s e 3) Ar'CH2X

CH2Ar' T e t r a h e d r o n (1975)

1 ) LDA

I1

------P

Me$ iCN

31 1 2 1 9 0

Ph-CHO t

SECTION 169

Q B r

Ph-CH CN

r

P h A c U

48 %

3) HC1

4 ) NaOH S y n t h e s i s ( 1 9 7 5 ) 180

a::: CuBr2

~50%

PhN02, A

JCS P e r k i n I ' ( 1 9 7 6 ) 2241

S y n t h e s i s ( 1 9 7 6 ) 416

SECTION 171

Me2C0 +

KETONES FROM AMIOES

PhCHO

KHFe(C0I4

263

MeCOCH2CH2Ph JCS P e r k i n I (1975) 1273

S e c t i o n 170

NO

Ketones f r o m A l k y l s and Methylenes

a d d i t i o n a l examples

S e c t i o n 171

Ketones f r o m Amides

JOC (1976)

41 3651

0

N( S02PhN02)2

T e t r L e t t (1975) 3107

70%

264

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 172

56%

1 ) MeLi 2) DMF

CNMe2

c1

1 ) MeLi

2) Me1

c1

&CH3

81 % C" 3

JOC (1976) 41 3651

Section 172

Ketones from Amines

Tetr Lett (1976) 1641

SECTION 172

KETONES FROM AMINES

JACS ( 1 9 7 5 )

8

265

97 6900

1 ) acetone 2 ) MCPBA

3) H30

%30%

0 A u s t J Chem (1975)

28

2547

97%

S y n t h Comm (1976)

6

285

266

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 173

CH31

CH3N02

i-AmN02

18%

JOC (1976) 41 153

dMe

Me bengal hu rose 02,

\

~

N-CHO

90%

i

Me

Me

Synthesis (1976) 255

S e c t i o n 173

0

Ketones from Esters

0

II I1

RCCH2C-OR

+

DABCO

xylene rfx

RCOCH3

JOC (1974) 3 2647

MeCH2COOEt

KH

THF

MeCH2COCH( Me)COOEt Synthesis (1975) 326

95%

SECTION 174

BuC02Et

26 7

KETONES FROM ETHERS AND EPOXIDES

Tho2 300"

BUCOBU

80%

B u l l SOC Chim France (1974) 1455

0

RCH2C-OR' II

0

several steps

II / R " R-C-CH \R" JACS (1975)

Review:

97 439

" R e a c t i o n o f Organomagnesium Compounds w i t h T h i o c a r b o n y l Compounds" B u l l Soc Chim France (1975) 1439

S e c t i o n 174

Ketones f r o m E t h e r s and Epoxides

86%

JACS (1976)

98

6717

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

268

SECTION 175

78%

Comptes Rendus

S e c t i o n 175

C

(1975)

280

791

Ketones from H a l i d e s

T e t r L e t t (1976) 3985

1 ) LDA, THF

Me2C=N

2 ) E-C8Hl7C1

t

S-CBHl7CH2COCH3

80%

3) H30 @ L i e b i g s Ann Chem (1975) 719

PhCHCOOH

I

Br

+

Zn

+

MeCN

-

MeCOCH2Ph

J Organometal Chem (1974)


139

269

KETONES FROM HALIDES

SECTION 175

91%

JACS ( 1 9 7 4 )

96 3250

RCH-C-R

/ R = 3"

RMgX

-+

1 eq. HMPA

co

30-50%

R2CHCOR

=

-----+

30 a t m

\

R = 2"

Mixtures

T e t r L e t t (1974) 3377

-n-C5H1,Br

+

Na2Fe(C0)4

+

1 ) THF

CH2CH2

2 ) HOAc

JACS ( 1 9 7 5 )

ArX

+ KCH2COMe

hv

NH3(1 1

ArCH2COMe

97

§5%

n-C5H,1COEt

6863

(SRN1 mechanism)

Chem Pharm B u l l (1975)

23

2621

2 70

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 3

SECTION 175

aEt uMgBr 1 ) Et3B

69%

r

2 ) MeCOCl

COMe

T e t r L e t t (1975) 4239

Review:

"Oisodium T e t r a c a r b o n y l f e r r a t e - A T r a n s i t i o n Metal Analog o f a Grignard Reagent" Accts Chem Res (1975)

8 342

66% c1

II 0

T e t r Lett (1975) 2767

JACS (1975)

97 3822

SECTION 175

271

KETONES FROM HALIDES

MeSCH2SOMe +

4,

1 ) KH

Br(CH2)3Br

76%

T e t r L e t t (1974) 3653

1

1 ) BuLi

30-40%

_____t-

*) R3

R4

T e t r L e t t (1974) 3295 Angew I n t Ed ( 1 9 7 4 )

277

1 ) BuLi, THF, -90"

90%

2 ) Ph2C0

3) Ho

Ph Chem B e r ( 1 9 7 5 )

0

-n-C6H131

+

II(-)

MeSCHSMe

-

108 2368

HC1

--+

'gH1 3C0C6H13

S y n t h e s i s (1974) 117

62%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

272

SECTION 176

0

S

CH2=C-CH2-S-C-NMe2 I/

I

OMe

1) LDA

r

/I

CH3-CCH2CH2Ph

98%

2) PhCH2Br 3) h y d r o l y s i s T e t r L e t t (1975) 4027

S

I1

1) NaOH, Me1

t

2) NaOH, Amy1 6 r

Me\ C/sCNMe2

Am/

NBS

C'N

Me

\

/"=O

Am

68%

T e t r L e t t (1976) 2967

SMe2 1 ) BuLi

( MeCO) *C=SMe2

2 ) PhCH2Br

I

II

PhCH2CH2COCCOMe

73%

JCS Chem Comm (1975) 239 Related methods:

Section 176

Ketones from Ketones ( S e c t i o n 177), Aldehydes from Hal ides (Section 55)

Ketones from Hydrides

This s e c t i o n l i s t s examples o f t h e replacement o f hydrogen by k e t o n i c For t h e o x i d a t i o n o f methylenes R2CH2 + R2C0 see groups, R H + R C O R ' . Section 170 (Ketones from A l k y l s and Methylenes)

KETONES FROM KETONES

SECTION 177

273

COCH3

H2N-C-NHCOCH3

51 %

polyphosphoric a c i d

*

OMe

@

OMe

Chem and I n d (1976) 1069

Review:

" F r i e d e l C r a f t s Acyl a t i o n " Chem and I n d (1974) 727

S e c t i o n 177

Ketones f r o m Ketones

T h i s s e c t i o n c o n t a i n s 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, k e t o n e t r a n s p o s i t i o n s and a n n e l a t i o n s , 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 r e d u c t i v e a l k y l a t i o n s o f enones 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 f r o m O l e f i n s ) .

&

L4g""

0'

Me I T e t r a h e d r o n (1974)

PhCH2COMe

RX, NaOH

phase t r a n s f e r catalyst

88%

t.

PhCHRCOMe

30

3263

high yields

T e t r L e t t (1975) 3757 JCS Chem Comm (1975) 393

274

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 1 7 7

NaNH2

90%

TH F S y n t h e s i s (1974) 201

7 8%

JOC ( 1 9 7 4 ) 2 7 3 2

6

0

t

PhCH2Br

JL To C,H P,

THF PhCH2NMe3F

JACS ( 1 9 7 5 )

97

3257

t Col 1 Czech (1976)

41 7 4 6

h

63%

SECTION 177

KETONES FROM KETONES

275

'gH1 1

1) LDA, HMPA

74%

2) t4eI S y n t h Comm (1975)

1) K-Selectride, 2 ) MeI, -78"

5 435

*P

THF

CMe=CH2

98%

CMe=CH2

JOC (1975)

JACS (1975)

1 ) LDA, THF

3

146

97 1619

&SPh

2 ) Me1

T e t r L e t t (1974) 3955

93%

276

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS

Rec T r a v Chim (1974)

JACS ( 1 9 7 4 )

"'yJ

LiO

t-Bu02C

96

93 153

3684

-H,oo

f 1

+.

SECTION 1 7 7

VOL 3

M~

JACS ( 1 9 7 4 )

90% HOOC

96 6 5 2 4

0'

SECTION 177

KETONES FROM KETONES

JACS (1974)

277

96 7573

JCS P e r k i n I (1976) 540

n

0 0 0 \ I HC-CH2-C-CH3

I

n 0

I

0

Bz

BzCl

\/

H-C-CH2-C-CH I 3

S02Ph

S02Ph

/ reduction,

hydrolysis, elimination

0

Bz

II

Bz-CH2-CH2-C-CH 3 CH3 B u l l SOC Chim France (1975) 1363

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

278

NNHTs

II

R-C-R'

+

NBS

25"

NaHS03 r

MeOH/Acetone

rfx

JOC (1974)

r

SECTION 1 7 7

75-91%

R

39 3504

4 4 "Me2

1 ) LDA

/

,Me

95%

2 ) Me1

t-BU

3) N a I 0 4

-t - B u

T e t r L e t t (1976) 3

73% 3 ) O3

(R) 87% e e

Angew I n t Ed (1976)

fi 549

SECTION 177

279

KETONES FROM KETONES

Q

1 ) BuLi ( 2 moles) 2)

65%

F

Br

-0

3) H30@

JOC (1976)

41 439

0 R-C-R'

+

(Ph3P)2 Pd02

II

benzene

74-98%

R-C-R'

T e t r L e t t (1974) 797

F o r t h e p r e p a r a t i o n o f enamines f r o m ketones see S e c t i o n 356 (Amine 01 e f in )

A 1,2-al k y l a t i v e c a r b o n y l t r a n s p o s i t i o n :

60-75%

JACS (1975)

97

439

280

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

,.&

1 ) /tOAc,

SECTION 177

TsOH

I

2 ) anodic o x i d a t i o n

NaBHq OH

%30%o v e r a l l Chem L e t t (1976) 1319

t-BuOH

65%

t-BuOK

Br JOC (1974)

2 573

2) Acid JACS (1975)

97

2218, 2224

SECTION 1 7 7

KETONES FROM KETONES

281

98

JACS (1976)

248

70% (second step) JOC (1976)

41 2918

75% Can be a l k y l a t e d f u r t h e r , dehydrosulfenylated.

JACS (1976)

98 5017

mBr ,

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 3

282

SECTION 177

Me2CuLi

____t

PhH

25%

,\"

0"

T e t r L e t t (1974) 2591

n 0

It

0

0

/ I l l

CH3CH2CCH CH CCH-P(OMe)2 2 / CH2CH=CHEt

NaH

68%

DME

___+

Et Synth Corn (1975)

Review:

5

1

"The Thermal Cycl i z a t i o n o f U n s a t u r a t e d Carbonyl Compounds" S y n t h e s i s (1975) 1

t

Ph

1

1

M

D

Chem E e r (1975)

P Ph h

108 2368

85%

SECTION 177

KETONES FROM KETONES

283

Et

Cf-iBu

He

E&

Comptes Rendus

&

91 %

C

(1975)

280

309

OSiMe3

400"

99%

~

Widely v a r y i n g y i e l d s w i t h o t h e r r i n g s i z e s .

JOC (1975)

40 858

0

Me

Q3

OH

45%

T e t r L e t t (1975) 1531

Me3A1/Ni ( acac)2 Et20

0 b

II

PhC( CH2)3Me

Aust J Chem (1975)

28 821

55%

284

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

0

0

It

II

CH3C-CH-C-CH2Li

I

Na

0 1 ) CH2i3r2

2) H ~ D @

+

.Q OTMS

OMS0

0

I1 II

CH2( CH2CCH2CCH3)2

JOC (1976)

A920

SECTION 177

29%

41 2772

r

61%

0

0

JACS (1975)

97 649

0 2 PhCOCH3

1 ) LOA, THF 2) CuC12, DMF

I1

JACS (1975)

Review:

83%

Ph-C-CH2CH2-C-Ph

97

2912

" I n v e r s i o n of Carbonyl R e a c t i v i t y " Chem and I n d (1974) 687

Review:

"The Use of K i n e t i c a l l y Generated U n s t a b l e E n o l a t e I o n s i n t h e R e g i o s p e c i f i c F o r m a t i o n of Carbon-Carbon Bonds" Pure and Appl Chem (1975)

43 553

Ketones may a l s o b e a l k y l a t e d and homologated v i a o l e f i n i c ketones ( S e c t i o n 374) R e l a t e d methods:

Aldehydes from Aldehydes ( S e c t i o n 49)

SECTION 178

S e c t i o n 178

KETONES FROM NITRILES

Ketones from N i t r i l e s

phxP

Me

1 ) Me3SiC1

1.70%

r

2) B r 2 3) Ag20 JOC (1974) 39 2799 T e t r L e t t (1974) 3029

JOC (1975) @ 267

74% J Organometal Chem (1974)

fl 139

73% i-bu

Comptes Rendus (1975)

280

889

2 86

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

I - ( CH2) 3CMe2CN

-

SECTION 179

Po

Ma

Et20

J Organometal Chem (1975)

Me3A1

PhCN

Ni(acac)i?

s;l 25

PhCOMe

80%

A u s t J Chem (1974)

S e c t i o n 179

79%

7 2577

Ketones f r o m O l e f i n s

0 RCH=CHR

1 ) HgS04, H20 2) @OH

r

II

RCCH2R

JOC (1974)

39

30-70%

3445

80% bOOEt

iOOEt JOC (1974)

2 2674

SECTION 179

KETONES FROM OLEFINS

Na2Cr207

287

82%

c

HQ Hg(OAc)2

0

JOC (1975) 40 3577

PdC12, CuCl

68%

DMF, O2

Tetr Lett (1976) 2975

JCS Perkin I (1974) 2169

80%

288

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 179

JACS (1975) 97 3822

0

JCS Perkin I (1975) 129

JCS Chem Comm (1976) 209, 210

JOC (1976) 41 265 JOC (1976) 41 273

KETONES FROM MISCELLANEOUS COMPOUNDS

SECTION 180

289

See a l s o s e c t i o n 134 ( E t h e r s and Epoxides f r o m O l e f i n s ) and S e c t i o n 174 (Ketones f r o m E t h e r s and Epoxides)

S e c t i o n 180

Ketones f r o m M i s c e l l a n e o u s Compounds

Conjugate r e d u c t i o n s and r e d u c t i v e a l k y l a t i o n s o f enones 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 f r o m O l e f i n s ) .

Br

0

OSiMe3

1) [ N ~ ( ~ P P P ) ~ C ~ ~ I

t

II

75%

PhCH2C-CH3

PhMgBr Chem L e t t (1976) 1239

CO, -78" N iE t 2 ( b w

THF

'

100% Et"\Et Chem L e t t (1976) 1217

%q+c+gq CH CH CCH3

CH2-SCNEtZ

211

0

H e l v Chim Acta (1976)

2

522

52%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

290

t-Bu-NIC -

SECTION 180

/Bu

t - B u-N=C

'Li

BuLi

1 ) electrophile

2) H202, NaOH

0

/Bu t B u-N=C

-

63%

Bull Chem SOC Japan (1975) 3 3682

Et3B + PhC=CH2

I

N3

1) H904 2) H202, NaOH

0

h-

A 11

Ph

9 5%

CH2Et

Tetr Lett (1975) 2195

65% Tetr Lett (1976) 2533

PROTECTION OF KETONES

SECTION l8OA

RCHR'

291

1 ) Me0

I

R

65-88%

R'

3) Me2S JOC (1974)

Section 180A

2 259

P r o t e c t i o n o f Ketones

This s e c t i o n covers k e t a l s , t h i o k e t a l s , and hydrazones. See a l s o Section 363 (Ether-Ether) f o r k e t a l s and Section 367 ( E t h e r - O l e f i n ) f o r enol ethers. Some of t h e methods i n Section 60A ( P r o t e c t i o n o f Aldehydes) a r e a l s o a p p l i cab1e t o ketones.

n

K

0

*

Ph TsOH

Ph

0

74%

JCS Chem Comm (1975) 432

0"" OEt

E t O H , HC(OEt)3

montmoril l o n i t e

B u l l SOC Chim France (1975) 2558

Synthesis (1976) 678

78%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

292

b

SECTION 180A

K

H@ benzene

+

+

or

T e t r L e t t (1975) 3775

R

R‘

\c=o

/

Br2C( CH20H)2 TsOH, benzene, r f x

R”

‘0

T e t r L e t t (1976) 4577

SECTION 180A

b

293

PROTECTION OF KETONES

MeS-TMS

Me?5

90%

No a c i d c a t a l y s t required.

JACS (1975)

97 3229

73-99%

R,R’

= H, a l k y l , a r y l , c y c l i c

Chem Pharm B u l l (1976)

3

1115

9 6%

T e t r L e t t (1976) 3667

T e t r L e t t (1976) 3

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

294

6

SECTION 180A

NNHTs

MOOCl

or WF6

74% S y n t h e s i s (1976) 808, 809

(5 NNHTs

72%

S y n t h e s i s (1976) 611

4

N

TiCl NaOAc/HOAc

t

2.90%

I

NHTs

0

Chem and I n d (1975) 87

NNHTs

acetone/H20

BF3. E t 2 0

S y n t h e s i s (1976) 456

83%

SECTION 180A

6

PROTECTION OF KETONES

295

NNHTs

Me2C0 A,

75%

sealed t u b e JOC (1975)

3302

98%

JOC (1975)

40

1502

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 13

PREPARATION OF

NlTRlLES

Section 181

Nitriles from Acetylenes

No additional examples

Section 182 BuCH2COOH

Nitriles from Carboxylic Acids and Acid Halides (cF3co)20

BuCrN

NaN02

60%

JOC USSR (1975) Section 183

11 653

Nitriles from Alcohols

H00cH20H NaCN

67%

DMF, 110°C

JOC (1976) 41 2502

Section 184 Ph

Nitriles from Aldehydes

+

Me-C-NEt

-BF4

Ph

' h CN

Synthesis (1 975) 401 296

56%

SECTION 184

297

NITRILES FROM ALDEHYDES

0

PhOSOCl ___c

CH=NOH

Et3N

R-CzN

92% S y n t h e s i s (1975) 502

+

Ph

Me2N=CH-SMe

\

+

phh Me2SCl

I-

Ph

/

71 %

C1-

FoH H

CN

Synth Comm (1975)

5 423

1) H+ C6H13CH0 + H2N0

2 ) -OH

91%

'gH1 3CN

iO*

JOC (1975)

40 126

90% T e t r L e t t (1976) 603

81 %

I

CH=NOH

Z Chem (1976)

16 17

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

298

3"''

NH2DSD3H

89% CN

RCHO

t

SECTION 184

NH20S03H

H20

65"

Helv Chim Acta (1976) & 2786

60-90%

RCN Tetr Lett (1974) 3187

MeCH=NOH t Me2N=CC12

Ph-CHO

RCHO

---+

-3

t

PhCH-NTs

RCH=NOH

rfx

C1-

CHCl 2-4 hr

NaCN

HMPA

DCC

cuc1*

RCEN

82-971

Synthesis (1974) 563

PhCEN

71%

Tetr Lett (1976) 1781

55-92%

RCN

(44 cases)

Et3N

Chem Ber (1 974) 107 1221

RCH=NDH + R'C(OEt)3

H+

290%

RCN JOC (1974) 2 3424

SECTION 187

299

NITRILES FROM AMINES 1 ) L i , Et2NH. HMPT

71%

Et2CH-CN

Et2CH-CH=NNMe2 2 ) $0

Synthesis (1976) 237 and 238 Ph

I

T e t r L e t t (1976) 2691

N i t r i l e s from A l k y l s , Methylenes and A r y l s

Section 185

No a d d i t i o n a l examples

Section 186

N i t r i l e s from Amides

RCONH2

Polymer-PC12

RCN JACS (1974)

96 6469

P h3P (OT f f PhCONH2

7 0%

PhCN

T e t r L e t t (1975) 277

Section 187

PhCH2NH2

N i t r i l e s from Amines

PhSeOC 1

85%

PhCN Synth Corn (1976)

5 285

COMPENDIUM OF ORGANIC SYNTHETIC MElHOOS VOL 3

300

S e c t i o n 188

SECTION 190

N i t r i l e s from E s t e r s

8 9%

Aust J Chem ( 1 9 7 5 )

S e c t i o n 189

8 1097;

2499

N i t r i l e s frm E t h e r s and Epoxides

No a d d i t i o n a l examples

S e c t i o n 190

N i t r i l e s from Halides CN

Br

68% Synthesis (1975) 605 Polystyrene CI

ri-C8H1 7Br

aq NaCN

n-C8H17CN

92%

CH2NMe2Bu C7 -

JACS (1975)

97

5956

CH2C12 Br(CH2)4Br + Et4NtCN

_____+

NC-(CH2)4CN

90%

Synthesis ( 1 975) 605

100%

JOC ( 1 974)

2 3416

SECTION 193

n-BuBr

NITRILES FROM NITRILES

NaCN Bu3N

301

n-BuCN

100%

-

Synth Comm (1976)

PhI + KCN

Pd(O) c a t +

6

193

PhCN

93% Chem L e t t (1975) 277 B u l l Chem SOC Japan (1975) (Pd I 1 c a t a l y s t )

S e c t i o n 191

48

3298

N i t r i l e s f r o m Hydrides

50% JACS (1976)

S e c t i o n 192

98 271

N i t r i l e s f r o m Ketones

No a d d i t i o n a l examples

S e c t i o n 193

N i t r i l e s from N i t r i l e s

R e d u c t i v e a l k y l a t i o n s o f o f u n s a t u r a t e d n i t r i l e s a r e found i n S e c t i o n 74 (Alkyls from Olefins).

96%

S y n t h e s i s (1975) 180

302

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

I ) M e L i , THF

PhCH2CN

F

2 ) Me1

SECTION 193

95%

PhC(Me)2CN T e t r a h e d r o n (1975)2 153

CH2=CHCH2CN

1 ) i--Pr2NLi

2)

98%

CH2=CHCH-CN

dr

T e t r L e t t (1975) 4647

Me,

NC

,CC' H2

+ H-C-CN

H20, NaOH

75%

NC

S y n t h e s i s (1976) 387

82% CN JOC (1976)

CN

C ( ~ - B U ) ~ B M ~ +I CCH2=CHCN U

41 1560

- TCN 88%

2 ) H20

T e t r L e t t ( 1 976) 255

PhCH2CN

E t B r , NaOH

phase-transfer c a t .

PhCHCN

I

Et O r g S y n t h (1976) 55 91

SECTION 195

303

NITRILES FROM MISCELLANEOUS COMPOUNDS

S e c t i o n 194

N i t r i l e s from O l e f i n s

Et4NF

Ph2C=CHN02

MeCN

NCCH2CPh CH NO

2

2

4 5%

2 S y n t h e s i s (1975) 162

Et4NtI-

( n - o c t y l )3B

2.50%

( n - o c t y l )CH2CN

+

CH3CN electrochemical rdxn

Chern L e t t (1975) 523

S e c t i o n 195

N i t r i l e s f r o m M i s c e l l a n e o u s Compounds N-OH

I1

HOOC-CH2-CH - C

‘COOH

PhNCO

HOOC-CH2CH2CN

93%

S y n t h e s i s (1976) 418

N=N

NaOBr iH Ph-NC

92%

-----+

NHPh Angew I n t Ed (1976)

113

n

%loo%

MeCN

JCS P e r k i n I (1976) 1901

304 NH

I1

Et-C-NH2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

S E C T I O N 195

CHC13, NaOt! phase-transfer c a t

F

.Et-CEN

2 Chew (1975)

84%

15 301

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 14

PREPARATION

OF OLEFINS

S e c t i o n 196

O l e f i n s from Acetylenes

OMe

I

LiA1H4

Me-C-CX-CH

I

CH2CH0

OH

ii,

93%

--------+

THF, r f x

-

A c t a Chem Scand

(1975)

609

1 ) BH3-THF 2 ) AgN03, H20,

72%

OH T e t r L e t t (1976) 4871

>95% c i s isomer

No y i e l d s , f e w d e t a i l s JCS Chem Comm (1975) 647

305

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

306

SECTION 196

8 5%

JCS Chem Comm (1976) 596

CH3-CrC-CH CH 2

PdC12, DMF 3

+

L-.

%loo%

Chein Ber (1976)

109 531

1 ) L-BIJ~A~II

C41i9- CsCH

2) L-BuLi

4 6%

3) BzBr

Bz Tetr Lett (1976) 1927

~

C

E

C + Et3B H

1 ) BuLi

2) Bu3Sf?C1

f

-

71%

Tetr Lett (1976) 805

73%

Tetr Lett (1976) 15

SECTION 196

307

OLEFINS FROM ACETYLENES

[Rh( NBD) (PP hMe2)3]f Me2C-C-CMe

t

acetone, H2

I

OH

,H

Me .C’

c=c, ‘OH

/H

97%

Me

JACS (1976)

2143

1 ) DIBAL

68%

2 ) CH3L-,’iBr

JOC (1976)

(

O

B

f

BuCXLi

41 2214

1 ) HC1

76%

2 ) 12/MeOH S y n t h e s i s (1975) 376

1 ) Me2S04 eiBu2CX6u Li+

H

+ BuH::

2 ) H+

74%

(83% E isomer) T e t r L e t t (1975) 1633

LJ JACS (1975)

MeC-CSMe + PhMgX

-

97 5249

wSMe

CuI

Me

THF

Ph

Rec T r a v Chim (1974)

9 5%

93 24

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

308

SECTION 197

100% JOC (1976)

1 ) [PrCuBrIMgBr PhC :C- H

+

2 ) H20

41 4089

Ph, pr/C=CH2

95% Rev T r a v Chim (1976)

95 299,

304

99% ‘Ph

JOC (1976)

S e c t i o n 197

Ph2CCH2COOH

I

OH

41 2241

O l e f i n s f r o m 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

DMF a c e t a l CHCl

Ph2C=CH2

88%

T e t r L e t t (1975) 1545

S y n t h e s i s (1976) 737

OLEFINS FROM ALCOHOLS

SECTION 198

1)

COOH

309

LDA

2, D

63%

o

3 ) SOC12/Py 4 ) 140' JOC (1974)

E t 3 k C P h + EtCOOH

-

2

1650

75%

EtCH=CHPh T e t r L e t t (1974) 2961

Pb( OAc)4 Me0

OMe

Cu( O A C ) ~ ,benzene

80% Me0 T e t r L e t t (1976) 2079

S e c t i o n 198

O l e f i n s from A l c o h o l s

1 ) PBr3, CuBr CH~=C CH( - OH)CH~~H

I

(CH2)2CH=CMe2

2) Zn

CH2=C-CH=CH2

I (CH2)2CH=CMe2

JACS (1975)

2 3252

58%

310

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 198

(TiC14 + LiA1H4) (PhCH ) C-CH2SPh

2l

OH

P

PhH, d i o x

R,N, J

( PhCH2)2C=CH

96%

Chem L e t t (1975) 871

Ph CMe2CHOHR

p-TsOH, PhH

RCH( Ph ) CMe=CH2

+

dark

high y i e l d

JCS Chem Comm (1975) 8211

CH3CH-CHCH3

I I

OH NO2

MeS02C1

67%

CH3CH=CCH3

I

Et3N

NO2 JOC (1975)

8

JOC (1976)

q''

(CH2

8

0

It

40 2138

85%

fl 896

1 ) Me2NPC12 2 ) Na, xylene

'

85%

( C H i a 90% c i s Synth Comm (1975)

3 293

A

1) L - P r I 2 ) Zn/EtOH

R

40-80%

/--

’

R

R

31 1

OLEFINS FROM ALCOHOLS

SECTION 198

m i x t u r e o f isomers JOC (1974)

39

3641

98%

90% c i s

Synth Comm (1975)

KH, THF PrCH-CHPr

I

SiMe,

\

5 293

96%

PrCH=CHPr

95% t r a n s HOAc

,

85%

PrCH=CHPr

97

5 HvH*seph JACS (1975)

1464

MeS0,Cl Et3N,

CH2C1

JCS Chem Comm (1975) 790

98%

31 2

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

96%

/Jc3H7

OHiM e 3 1

C3H7

C3H7

1H2S04/THF

n

C3"7

SECTION 199

99%

C3H7

T e t r L e t t (1974) 1133

S e c t i o n 199

O l e f i n s f r o m Aldehydes

I

PhCHO + Ph3i)CH2Ph

t-BuOK +

PhCH=CHPh

96%

CHZC12 9 18-crown-6 S y n t h e s i s (1 975) 784

(Et0)2P(0)CH2Ph

1 ) BuLi

i-PrCH=C-Ph

I -. LI

2 ) CC14 3 ) 1-PrCHO

69%

S y n t h e s i s (1972) 658

+

Ph3PCH3 + PhCHO

PhH NaOH/H20

PhCH=CH2 T e t r L e t t (1974) 2587

95%

SECTION 199

OLEFINS FROM ALDEHYDES

t

( CH2)4CH=PPh3 + L-ClOHz1

-

CHO

31 3

(CH2 )4CH=CH(CH2)9CH3 94% (E)

T e t r L e t t (1974) 207

50% aq NaOH

PhS02CH3 + PhCHO

86%

PhS02CH=CHPh

---f

CH2C12, TEBA

S y n t h e s i s (1975) 453

02NCH2CH2COOEt

PhCHO

PhMi:ZCOOEt

n-BuNH2, E t O H

>

2

H

J P r a k t Chem (1975)

PhCH=CH2 + PhCONHCHCOOMe

I

OMe

1 ) H2S04, PhH

45%

317 337

PhCH=CHCH( NHC0Ph)COOH

+

2 ) NaOH

42%

T e t r L e t t (1975) 3737

MeCOCH(OMe)SO2Ph

1 ) NaH -----+

2 ) CH20

O ,Me CH =C ‘S02Ph

7 5%

L i e b i g s Ann Chem (1975) 1484

PhNHS02CH2COOH i-PhCHO

Py, NH40Ac +

PhMe, r f x

PhNHSO CH=CH-Ph 2 S y n t h e s i s (1975) 321

67%

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 3

314

1 ) Me,SizHHex+Li J

Hex-CHO

2 ) H30+

/"\Hex

+

45%

Hex

Angew I n t Ed (1976)

TiC14-LiA1 H4

&'"O

SECTION 199

"proton sponge"

retinal

161

+

94%

@-carotene

r

90%

Chem L e t t (1976) 1127

retinal

+ LiA1H4 + TiC13 (RCHO

--+

---+

carotene

85%

RCH=CHR) JACS (1974)

PhCHO

H2CCa212

96 4708

Ph,

11%

H/C=CH2

Bull Chem

SOC Japan (1976)

2 1177

53%

NaOAc JOC (1976)

41 574

OLEFINS FROM ARYLS

SECTION 200

MeS-(&

BuLi

b

P

h

31 5

Ph-

d

46%

2) P h / V C H 0

+':6

T e t r L e t t (1975) 2861

Br

~

Br CHO

IiOAc, BzNH2

60%

rfx

c1 B u l l Chem Soc Japan (1975)

S e c t i o n 200

a 1091

Olefins from Aryls

1 ) PhIC12/hv 2) saponification 3) a c e t y l a t i o n

& 'OAc

JACS (1975)

97

6580

54%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

31 6

SECTION 203

A l k y l s and A r y l s f r o m A l k y l s and A r y l s ( S e c t i o n 65)

R e l a t e d methods:

A l k y l s and A r y l s From O l e f i n s ( S e c t i o n 7 4 )

S e c t i o n 201

O l e f i n s f r o m 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 f r o m Amines

1 ) Me1 CH CH OCHPh2

l2

2 ) anion-exchdnge r e s i n

*

H2C=CHOCHPh2

3) A

NMe2

Org S y n t h (1976)

S e c t i o n 203

PhCOOEt

3

Olefins from Esters

xs Ph,P=CH,

’

DMSO

+

56%

PhCMe=CH2 T e t r L e t t (1975) 1439

t-Bu -

Me-do Me

Coll idine

t-Bu-

;t

a

\c/-

t-Eu

58%

II

’-t-Bu

H

JCS P e r k i n I (1976) 884

SECTION 204

Review:

OLEFINS FROM E P O X I O E S

O l e F i n s v i a Phosphonates

S e c t i o n 204

31 7

Chem Rev (1974)

74 87

O l e f i n s f r o m Epoxides

53%

40 2555

JOC (1975)

/Jpr Pr

H.

..A, 0

/

Me3Si

,J

\C3H7

acid

LiCuPr2

-90% Pr

Pr

m

Pr

JOC (1975)

2263

Pr

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

31 8

0

PhSi Me2Li

____,

' i 4 - P h Ph H

n

75%

Ph

Ph

SECTION 204

Synthesis (1976) 199 Me

I

100% Synthesis (1976) 200

100%

JCS Perkin I (1975) 1216

Ewi

Me3SiSiMe3

H

Et

86%

KOMe JACS (1976)

3

1265

SECTION 205

OLEFINS FROM HALIDES AND SULFONATES TiC14-LiA1 H4

~

\/=TT

f

CH2CH2Ph

ether

31 9

CH2CH2Ph 9 5%

Me Chem L e t t (1976) 737

N2CHCOOE t

phHph

94%

H

H

JACS (1975)

97 2553

OTMS

I

1 ) BH3, THF

76%

2 ) aq HC1 T e t f L e t t (1975) 4005

S e c t i o n 205

O l e f i n s f r o m H a l i d e s and S u l f o n a t e s

t-BuOK

Br

RCH2CH2Br

1 ) o-N02C6H4Se2 ) H202, THF

x

84%

S y n t h e s i s (1974) 190

RCH=CH2

JOC (1975)

40 947

320

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 2 0 5

o<:r 0 Na2S204

60%

DMF

A c t a Chem S c a n d

+

1 ) EtOH

CH3(CH2)11Br

2 ) H202, THF

JOC ( 1 9 7 5 )

Me2C=CHCH2P0 (OEt ) 2

Octyl Br BuLi

(1976)

30

CH3(CH2)9CH=CH2

366

%

70%

40 947

Me2C= CHCH- PO( O E t ) 2

I

g

LiA1H4 -3

Octyl 94%

Et20

O0

/"

Me CH-Cr=C

2

H

a4 %

HO

Angew I n t Ed ( 1 9 7 4 )

,-:;-;

13 4 0 7

95%

Br t

Br

Col 1 Czech (1976)

41 2 0 4 0

OLEFINS FROM HALIDES AND SULFONATES

SECTION 205

-C-C-

I

+ 2e

I

el ectrochemical red

321

+

-trans *

periplanar elimination high yield

JOC (1974)

2 2408

81 %

LOOH

JOC (1976)

41 4035 81 %

Synthesis (1 976) 607

aoBr 8'

NMe2 NMe2

Synth Comm (1975)

n-C8H1 7CHBrCH2(0H)

TiC14-LiA1H4

+

5 87

n-C8H17CH=CH2 J O C (1975)

92%

9 3797

74%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

322

'V Yh /- \ Br

SECTION 205

NaI, H20

C1 2HC-CHC1 phase-transfer catalyst

Br

89%

Ph

9

Synthesis (1975) 397

100% I

Br

Et2CH-CHCC13

I

Synth Comm (1975) 3 87

B u L i , -50"

OMe

E t,O/THF

F

Et2CH-CH=CC1

75%

L

J. Organometal Chem (1975)

PhCHBrCHBrPh + R4Pt6r-

Na2S203 + NaI H20/PhMe 90%

PhCHZCHPh

97 355

86%

Synthesis (1975) 397

i-Pr

SiMe3

Y H 2 C I

Bu

CuLi

i-Pr

SiMe3 CH2Bu

Tetr Lett (1976) 4439

80%

SECTION 2 0 5

OLEFINS FROM HALIDES AND SULFONATES

0 4

PhSCH2Ph

f

RCH2X

LiICA

r Fx

323

RCH=CHPh JOC ( 1 9 7 5 )

2014

0

II

Ph

rPh

Li

hp’

64%

JACS ( 1 9 7 5 )

RCH2Br

f

PhSe-Na

-

RCH2SePh

1 ) L-Pr2NLi 2 ) R’CH2Br

3 ) H202

97

3250

R

HH

H

60-80%

R’

JCS Chem Comm ( 1 9 7 4 ) 9 9 0

/=(

MgBr

n-PrI

97%

n-Pr

-

T e t r L e t t (1976) 3225

324

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

+

PhCH2AsPPh3

I

br

1 ) NaH, THF 2 ) PhCHO

+

P h C H = C H e E i r

50%

J Organometal Chem (1975)

B r a C H 2 B r

SECTION 207

1 ) Ph2P

98%

2) CH20, H20, -OH Synth Comm (1976)

96 237

6 53

100%

T e t r L e t t (1974) 3809

Section 206

O l e f i n s from Hydrides

No a d d i t i o n a l examples

Section 207

O l e f i n s from Ketones

37-72% 0

JCS P e r k i n I (1975) 809

OLEFINS FROM KETONES

SECTION 207

325

4 4 1 ) B2H6, THF

76%

T e t r L e t t (1975) 4005

21 ) C1PO(OPh)2 LDA

59%

c

3 ) (E-Bu)2CuLi

T e t r L e t t (1976) 4405

SiMe3

ti

I

P r - -CH-n-Amyl

0

bC

H

Pr

1 ) MeLi

2 ) H30+

3)

L-BuOK

’

Me

!-Amy1

91% s t e r e o s e l e c t i v i t y JOC (1976)

I. Q

59%

ffl 2940

1 ) C-BuLi

67%

PPh20

2,

JCS P e r k i n I (1976) 2386

COMPENDIUM

326

Ph

OF ORGANIC

SYNTHETIC

METHODS VOL 3

AA

SECTION

207

7 2%

NaOAc

JOC (1976)

41 574

NaBH3CN 79%

JOC (1975)

MeCH2C=NNHTs

I

1 ) B u L i , TMEDA 2 ) Me1

Ph

*

40 923

MeCH=C-Me

95%

I

Ph T e t r L e t t ( 1 9 7 5 ) 1811

100%

Org React ( 1 9 7 6 )

3 405

0" -70 NNHTs

Na/EG

Org React (1976)

100%

23 405

SECTION 207

327

OLEFINS FROM KETONES

Tetr Lett (1976) 4041

1 ) Me3SiCHHex

Li'

2 ) H30t

+

tex Anyew I n t Ed (1976)

40%

5 161

47%

Tetr L e t t (1975) 2861

C1 CHEW(O E t ) 2

1 ) BuLi, LiCl

0

77%

2 ) CC14

3,

cc1

0

Synthesis ( 1 975) 535

328

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 207

T e t r L e t t ( 1 9 7 5 ) 1373

+

Ph3PCH=CH2

+

>go%

HCH2SnMe3 JCS Chem Comin (1975) 630

72%

JOC (1976)

5 1735

T e t r a h e d r o n (1974)

30

2961

SECTION 207

(E t o ) 2P (0)CH2SOMe

1 ) B u L i , THF, -78"

MeCOCHzSiMe3

1 ) LiCH2CN +

84%

MeSOCH=CPh2

2 ) Ph2C0

JOC (1975)

.lo 1979

75%

MeC=CH2

I CHzCN

2) Ht

S y n t h Comm

Review:

329

OLEFINS FROM KETONES

1975)

2 15

B i s - W i t t i g R e a c t i o n s i n t h e S y n t h e s i s o f Nonbenzenoid A r o m a t i c R i n g Systems S y n t h e s i s ( 975) 765

TiC14-LiA1H4 " p r o t o n sponge" 94%

Chem L e t t (1976) 1127

Hex - CHO

1) MeSeH

3

Hex$

2 ) BuLi, Hex-CHO

2.65% Hex

3 ) TsaH, p e n t a n e / r f x

T e t r L e t t (1976) 1385

-.50% Ph

Ph

T e t r L e t t ( 1 976) 3265

330

COMPENOIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 209

active T i o

85% JOC (1976)

Ph2C0

L i A1 H4 T i C1

+

41 896

95%

Ph2C=CPh2 JACS (1974)

Review:

96 4708

Organic Chemistry o f Low Valent Titanium Accts Chem Res (1974)

Section 208

O l e f i n s from N i t r i l e s

No a d d i t i o n a l examples

Section 209

O l e f i n s from O l e f i n s

L

281

SECTION 209

331

OLEFINS FROM OLEFINS

3 ) -OH

T e t r L e t t (1975) 2709

O

r

\

A 91 %

DMF

a --a Org React (1975)

22

1

7 0"

100%

H

Org React (1975)

22

1

1 ) Ph2PLi 2) AcOH-H202

7 6%

3 ) NaH, DMF

JCS Chein Comm (1974) 142

1 ) BuLi, TMEOA

71%

2) PhCt12C1 CH2Ph T e t r L e t t (1975) 3047

332

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

TMS-C=CH2

I c1

-t-BuLi

SECTION 210

TMS-CH=CHBU

85%

-

CH2=CH2 + CH2=C(Me)CH2MgX

J Organometal Chem ( 1 974)

fl C9

MeCH2CH2C(Me)=CH2

Et20

75%

Liebigs Ann Chem (1975) 103; 119; 1176

CH2=CH2

1 ) t-Bu2Zn, PhH 2) HC1

+

CH =C

, Me

‘Bu-t

70%

Liebigs Ann Chem (1975) 1162

Section 210

Olefins from Miscellaneous Compounds LwOSiMe

2-t-Bu -

22%

t-BuMe2Si0

JOC (1976) 41 3947

SECTION 210A

Hex

I

H-C-C-Pr

PROTECTION OF OLEFINS

-

Pr

I

I 1 MeSe OH

Et3N

333

6 5%

H

Pr T e t r L e t t (1976) 3743

CH( CH3) SPh

1 ) CF3S03CH2C02Et 2 ) 50",

57%

DMF T e t r L e t t (1976) 3487

KOAc, 95% E t O H

PhCH2N02

PhCH=CHPh

d

JOC (1975)

Review:

9 187

Methods f o r t h e P r e p a r a t i o n o f Bridgehead O l e f i n s Angew I n t Ed (1975)

S e c t i o n 210A

14 528

Protection of Olefins

The p r o t e c t i o n of i s o l a t e d d o u b l e bonds i s c o n s i d e r e d i n t h i s s e c t i o n .

334

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VQL 3

SECTION 21OA

NaSPh

I n d i v i d u a l y i e l d s >95%

S-Ph .(

0

JOC (1975)

t r a c e HOAc

9 1181

5 e P h T e t r L e t t (1974) 1869

S t a b l e t o halogens, Hg(OAc)*,

c a t . H2, e t c . JACS (1975)

97

3254

SECTION 210A

PROTECTION OF OLEFINS

335

1 ) Me1

2 ) NaHC03

,%60%

40% T e t r a h e d r o n (1976)

R

( w

(PhHC=CH-C-CH3)Fe(

Ac Ac

32

c0)3

765

b

Fk(CO)3

P r o t e c t s t h e d i e n e system so t h e s i d e c h a i n d o u b l e bond can be h y d r o x y l a t e d by Os04.

Removed w i t h FeC13.

J Organometal Chem (1975)

S e c t i o n s 211 t o 299 a r e r e s e r v e d f o r f u t u r e a d d i t i o n s (e.g., of n i t r o compounds).

102 507

the preparation

Compendium of Organic Synthetic Methods, Volume3 Edited by Louis S. Hegedus, Leroy Wade Copyright 0 1977 by John Wiley & Sons, Inc.

Chapter 15

PREPARATION

OF DIFUNCTIONAL COMPOUNDS

S e c t i o n 300

Acetylene

-

Acetylene

1 ) BuCzCLi. THF

90% JCS Chem Comm (1975) 857

2.30%

Org Synth (1974)

1) H e x - C X - L i

(QBshe

2 ) Bu-CX-Li

'

54

1

Hex-CS-CX-Bu

T e t r L e t t (1976) 4385 336

61 %

ACETYLENE - ALCOHOL

SECTION 302

S e c t i o n 301

Acetylene

-

Carboxylic Acid

-

Alcohol

337

No a d d i t i o n a l examples

S e c t i o n 302

HCXH

Acetylene

1 ) BuLi, THF, -78" c

2) Me2C0

Me2C-CrCH OH

JOC (1975)

MeCXH

1 ) BuLi, TMEDA

2) BuBr, hexane

94%

I

40 2250

BuCH2CrCCH20H

+

3 ) CH20

JCS Chem Comm (1975) 817

C:CBu THF, PhMe,

0

+ BuC-CA1Et2

n-C6H14

65%

'OH

,

' , =CBU

JCS Chem Comm (1975) 287

63%

3 38 S e c t i o n 303

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3 Acetylene

-

SECTION 306

Aldehyde

Ph

60% ( l a s t step

Org Synth (1976) Section 304

Ph-C-C-MgBr

Acetylene

52

- Amide 0

1 ) Me2SiNC0

2) H20

55

+

Ph-CzC-!-NH2 T e t r L e t t (1975) 981

Section 305

Acetylene

- Amine

No a d d i t i o n a l examples

Section 306

HCSCCH~OH

Acetylene

-

- Ester

HCzCCH20THP

1) NaNH2

2) AcO ,

+

AcOCsCCH20H

3) HtL

Synthesis (1974) 357

*40%

SECTION 307

ACETYLENE

3) Me1

0

I1

Pr-C-CH2-COOEt

-

ETHER, EPOXIDE

JOC (1975)

1 ) H2NNH2 2) T1(N03)3, MeOH

339

40 269

Pr-CrCCOOCH3

Q55%

Org Synth (1976)

55 73

53%

T e t r L e t t (1975) 3337

Section 307

HCECOEt

Acetylene

1 ) LiNH2

-

Ether, Epoxide

HCH(OH)CH2CrCOEt

90%

1) TsC1, KOH 2) KOH

A

b

Rec Trav Chim (1974

CH2=CHC=COEt

7 4% 93 92 -

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

340

Section 308

-

Acetylene

SECTION 309

Halide

0

II

1) NaH, THF

(Me2N)2PCH2C-CH + p B u I

BuC:CCH2Br

2) PBrj

~70%

Synthesis (1974) 730

Et2NLi

CH-CCl

c=c-c1

Et20, THF

8oX

Synthesis (1975) 458

+ 2 Ph3PBr2

HOCH2-C:C-CH20H

MeCN

BrCH2-CX-CH2Br

92%

Synthesis (1975) 255

Section 309

Acetylene

PhCOCN + PhC-CLi

-

Ketone

Et20

-70'

PhCOCfCPh

61%

Bull SOC Chirn Fr (1975) 779

TMSCzCH

1) CuI,

t-BuOLi

2 ) PhCOCl

TMSCzCCOPh

JOC (1975) 40 131

66%

SECTION 311

ACETYLENE

0 Ph-C-C-Cu

+

-

0

I1

II

C1-C-CH2CH2-C-OMe

-

OLEFIN

34 1

5 2%

Ph-CzC Comptes Rendus

C ( 1976) 282 277

0

OH

I

H-CZC-CH-Ph

n i c k e l peroxide

II

98%

H-CZC-C-Ph

+

JOC USSR (1974)

S e c t i o n 310

Acetylene

lo 2081

- Nitrile

No a d d i t i o n a l examples

Section 311

Acetylene

00

- Olefin

t RCrCMgBr

---+

G

soc12

Ber (1974)

n-Bu, Et

c,=c,

/H

Cu.MgX2

t E-BuCZCH

Et20/THF

70-80%

107 2985

E-Bu,

_ _ _ _ +

TMEDA

-R

Et

,c=c

H,

'czc-Bu

T e t r L e t t (1975) 1465

78%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

342

n-Bu,

Et

,c=c

H, 1‘

+

~-BUCECCU

PY

Bu.

80-looo

Et’

SECTION 312

c-c /H

85%

‘C-C-Bu

J Organometal Chem (1975)

93 415

4 5%

I

Et Comptes Rendus

S e c t i o n 312

PhCH(COOH)2

Carboxylic Acid

C

(1976)

282 277

- Carboxylic Acid

1 ) 3 BuLi, THF, -50’

2) Me1

PhC(Me)(COOH)2

t

88%

T e t r L e t t (1975) 707

BrCH2CH2Br + CH2(COOEt)2

50% NaOH

TEEA

A

(COOHI2

7 5%

J Org Chem (1975) 40 2969 COOH

R

Q*

MeOMgOC02Me

93%

c

R JOC (1 974)

9 1676

SECTION 313

-

CARBOXYLIC ACID

JOC ( 1 975)

Section 31

0(r3

Carboxylic Acid

-

343

ALCOHOL

9 1488

Alcohol

CH2C12, NaOH/H20 Et3BzNt

-C1

68%

' S y n t h e s i s (1976) 825

OH

I

N a O W

0 Ph- CH-C- S

I

OH

.CH3

/*-Nti40H

PhbHCOOH

65%

Ph-CH-CONH2

71 %

P

I

55% OAc

JACS (1975)

97 596

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

344

P h2C=C( OTMS ) 2

1 ) MCPBA 2 ) H30t

'

Ph2C-COOH

SECTION 3 1 3

81%

I

OH JOC (1975)

40 3783

Ph

1) B u L i

2) RCHO

3) H30t

~ 7 7 %y i e l d

P

O

o

H

~20% optical yield

T e t r L e t t (1974) 1333

Me3SiCH2COOH

1) 2 i-Pr2NLi

CH2 (OH) CH2CH (SiMeg) COOH

+

94%

JCS Chem Comm (1975) 537 OSiR3

I

1) LiN( i-Pr)2 2) R3SiC1

h

94%

HO- - L O O "

T e t r L e t t (1974) 2027

SECTION 315

CARBOXYLIC A C I O

Section 314

Carboxylic A c i d

-

Aldehyde

-

Amide

-

345

AMIOE

No additional examples

Section 315

Carboxylic A c i d

Rh-DIOP

on polymer

,C02H PhCH=C

c

/Cop

H2

‘NHCOCH~

‘NHCOCH~

81% ee JACS (1976)

,H

Ph”

%loo%

PhCH2CH

98 5400

n

C

NyNH

____+

H20, r f x

Ph-CH2-CHCOOH NHCOPh

74%

I

Ph

T e t r L e t t (1975) 4051

HO-CH-C02H

I

HN-COPh

PhH

Ph-CH-C02H

___+

91%

I HNCOPh

H2S04

JCS Chem Comm (1975) 349

HO-CHCOOH + Me2CHSH

I NHCOPh

--

H2S04 HOAc

Me2CHS-CHCOOH

-80%

I NHCOPh

Tetrahedron (1975)

31 863

346

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

Section 316

Carboxylic Acid

-

SECTION 316

Amine

Review: "Advances in the Synthesis and Manufacture o f a-Aminoacids" Russ Chem Rev (1974)

Q< H

OOMe

43 745

0 0 t

II II

HO-C-C-CHRR'

t

H~N+

CHRR' b

coo-

H

>90% ee up t o 60% yield

R

,OTMS

I

HOOC-CH-NH2.HC1 + H3C-C %NTMS

JCS Chem Comm (1975) 988

1 ) THF 2)

H~O

R

I

H2N-CH-COOH

s95%

Synthesis (1975) 113

Me2NCH2COOH

1) L i t naphtha1 ide 2) PhCH2C1

PhCH2-CHCOOH

1

NMe2

CompteRendus (1974) 287 1383

60%

SECTION 316

Me2CHCH2COOH

-

CARBOXYLIC A C I D

1 ) 2 LDA 2 ) MeONH2

3) H30t

c

AMINE

347

’i

Me2CH HCOOH

33%

NH2 Chem Pharm B u l l (1975)

23 167

0

II

Ph-CH2CSC8H17

c02 Schrauzer’s complex Na2S204, NaHC03

7 3% PhCH2CHC00H T e t r L e t t (1976) 4343

1) -H20

0

II

CH3-C-COOMe + L-Phe-0-t-Bu

2) H2, Pd/C

+

*

CH3-CH-COOH

1

2 ) L-BuOCl

NH2 70% ee ( L predominates) T e t r L e t t (1976) 997; 1001

1 ) LDA 2 ) n-octyl iodide

Ph L

N

3 ) LDA

i-Pr, c -

H~N’

c

,C-Oct ‘COOH

5) H30t JOC (1976)

fi 3491

58%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

348 Section 317

Carboxylic A c i d

COOH

1 ) LDA

2) C l C O O E t

*

-

SECTION 319

Ester

Hoo?500Et

88%

T e t r L e t t (1974) 2721

Section 318

Carboxylic Acid

-

Ether, Epoxide

-

Halide

No a d d i t i o n a l examples

6

Section 319

Carboxylic A c i d

C 6 O O H

c12,02

,

C1S03H

73%

chloranil JOC (1975)

RCH-COOH + NaN02

I

NH2

+

(HF)xF-PyH+

-

40 2960

RCHCOOH

i

F Synthesis (1974) 652

CARBOXYLIC A C I D - HALIDE

SECTION 319

349

30%

JOC (1975)

5

1640

6 0%

Angew I n t Ed (1976)

306

____+

2 ) NCS OMe

__f

OMe 90% COOH

OMe

JOC (1975)

40 3158

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

350

SECTION 320

87%

JOC (1975)

1) S0Cl2

n-BuCH2COOH

-

2) (CH2C0)2NBr, HBr

9 3420

n-BuCH-COC1

+

- 1 Br

Org Synth (1976) 1 ) NCS

RCH COC 1

2) S0Cl2, HC1

*

~70%

55 27

RCHClCOCl

2.80%

Tetr Lett (1974) 3225 Also via: Haloesters (Section 359)

Section 320

Carboxylic Acid - Ketone

MeSCH=CHCMeCOOMe

I

CH2C:CH

HC1 -HOAC rfx

VooH

93%

0

Tetr Lett (1975) 405

CARBOXYLIC A C I D

SECTION 322

1 ) LOA 2 ) R3SiC1

t-

1)

-

OLEFIN

o3

351

COOH

2 ) Me$

90%

T e t r L e t t (1974) 2027

H2S04

MeCOCH2COOMe + PhCONHCH( 0H)COOH

MeCOCHCOMeCH( NHC0Ph)COOH

71 %

JCS Chem Comm (1975) 905

Carboxylic Acid

S e c t i o n 321

PhCOCl

+ NaCN

-

phase t r a n s f e r c a t . , CH2C12

Nitrile

*

60%

PhCOCN

T e t r L e t t (1974) 2275

Also v i a :

Cyanoesters ( S e c t i o n 361)

S e c t i o n 322

-

Carboxylic Acid

Olefin

no 5 E

C

O

O

H

JCS P e r k i n I (1974) 2005

90%

352

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

PhCH2COOH

1 ) R2NLi

F

2) PhCH2CH2Br 3) NaI04, 120"

SECTION 322

PhC-COOH

84%

II

CH2 JCS Chem Comm (1974) 135

Me3SiCH2COOH

1) 2 LDA

2) PhCHO

88%

PhCH=CHCOOH JCS Chem Comm (1975) 537

1) LDA ( 2 moles) 02H

2)

80%

/wBr

3 ) H30+

JACS (1976)

Me2C=CHCH2S02CH2COOMe

-t-BuOH KOH,

CC14

F

4925

Me2C=CHCH=CHCOOH

80%

Synth Comm (1975) 5 315

H2C=CHCH=CH2 + t-BuCu, MgBr2

co2

t-BuCH2CHCH=CH2

-

1

COOH

J Organometal Chem (1975) 92 C28

95%

SECTION 323

q

6

'

1

ALCOHOL

-

3

*

1 ) LDA

Yo

H02Ch

6

'

1 3

80%

2 ) t-BuSC1

0

>98% E

3 ) H30i JOC (1974)

Also via:

353

ALCOHOL

2

3315

Hydroxy a c i d s ( S e c t i o n 313) O l e f i n i c amides ( S e c t i o n 349) O l e f i n i c e s t e r s ( S e c t i o n 362 O l e f i n i c n i t r i l e s ( S e c t i o n 376)

S e c t i o n 323

Alcohol

-

Alcohol

...........................

1,P-Diols. O t h e r Diols.

............................

.page 353-355 355

HoTfY

1) Tl(OAc)3, HOAc 2 ) KOH, MeOH

HO

4

JCS P e r k i n I (1976) 1660

'

I ) HUHc, 12,

KI03

82 %

4 HO Gazz Chirn I t a l (1975)

105 377

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

354

dioxane

SECTION 323

ru rnn

JOC USSR (1976)

12 1234

0-

79%

T e t r L e t t (1976) 1973

b

Mg ( Hg ) T i C1

t

J O C (1976)

MeMg I

75%

t

41 260

d:;

100%

'Me

'Me T e t r L e t t (1974)

30

1397

SECTION 323

ALCOHOL

m/

-

1) Na2S204 2 ) NaI04

d i l . HN03

HO

'

NaN03

355

ALCOHOL

3 ) K I , NaHS03

HO

b

2.50% total

HO

HO OH

S t e r o i d s (1976)

2 733

1 ) LDA L

2)

oxazol i n e

eBr

~~0~

TMS-OW H

'

92%, 72% ee

JOC (1975) 4 21186 Also via:

H y d r o x y e s t e r s ( S e c t i o n 327) D i e s t e r s ( S e c t i o n 357)

356 Section 324

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3 Alcohol

-

SECTION 324

Aldehyde

eM-)( N

H'

c-;;"

H\ob HW1

I

JOC (1975)

40 2025

55%

Angew I n t Ed (1976)

2 169 57%

JACS (1975)

Also v i a :

Acetoxyladehydes ( S e c t i o n 336)

97

2232

SECTION 325

ALCOHOL

S e c t i o n 325

Alcohol

-

-

AMIDE

357

Amide

. . . . . . . . . . . . . . . . . . . . . . . . page .......................... ........................

a-Hydroxyamides. 6-Hydroxyamides. O t h e r hydroxyamides.

(i--Pr)2NCH0

1 ) LDA

92%

Ph2C-CON(i--Pr)2

I

2 ) Ph,CLO

OH

Can J Chem (1974)

52 185

- cl1 ) LDA

CONMe2

357 357-358 359

CONMe2

2 )‘ 0, L

84%

OH

3 ) Na2S03

T e t r L e t t (1975) 1731

b

0

I1

HO

CONH2

1 ) Li-C-N(CH20Me)2

44%

2 ) H30t

Me2CHCONEt2

Angew I n t Ed (1976)

-

1 ) LDA 2 ) PhCHO

5 293

85%

PhC(OH)HCMe2CONMe2 Comptes Rendus (1975)

281 893

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

358

0

SECTION 325

OH

II

I

yeast

Ph-C-CH2CONH2

___+

26%

Ph-$H-CH2CONH2

high optical p u r i t y A l s o works w i t h a - k e t o a m i d e s A u s t J Chem (1976) 2 9 2 4 5 9

88%

Can J Chem ( 1 974)

Ph

N-CH3

I CH3

__+ hu

0

52 3206

&yH3

%70%

I JCS Chem Comm (1974) 743

90%

i- P r 2

JCS P e r k i n I (1976) 2054

SECTION 325

t TsNClNa

ALCOHOL

-

AMIDE

359

64%

4

-t-BUOH JOC (1976)

fi 177

c

2 ) H20/NaHC03 Me3Si0

BzO OBz

BzO

OBz

93% on 10 Kg s c a l e JOC (1974)

2 3654

39 3660 ( u r a c i l s ) 39 3664 ( d i s a c c h a r i d e s ) 39 3668

3 3672

(5-azacytidines)

G l y c o s i d a t i o n o f P u r i n e s u s i n g SnC14/C1CH2CH2C1 T e t r L e t t (1974) 2141

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

360

S e c t i o n 326

Alcohol

-

SECTION 326

Amine

93% JACS (1975) NC

I

97

2305

1) BuLi

3 ) CH30H

~+ OH

Me

74%

NH2

Me

Ph

Ph

L i e b i g s Ann Chem (1976) 183 1 ) Me3SiCN RCOR'

OH

Zn12 +

2 ) LiA1H4

I

R-C-CH2NH2

I

R'

JOC (1974)

2 914

Ph Ph2C=NOH

1 ) BuLi 2 ) CH30H, H20

I

63%

Ph-C-NHOH

I

BU

T e t r L e t t (1976) 233

Review:

Methods o f S y n t h e s i s o f P y r i m i d i n e Nucleosides Russ Chem Rev (1973) 494

SECTION 327

Review:

ALCOHOL

-

ESTER

361

The S i l y l Method o f S y n t h e s i s o f Nucleosides and N u c l e o t i d e s Russ Chem Rev (1974) 140

as condensing a g e n t i n p o l y n u c l e o t i d e s y n t h e s i s . JCS Chem Comm (1974) 325

S e c t i o n 327

Alcohol

-

Ester

........................

a-Hydroxyester. B-Hydroxyester. . . Other h y d r o x y e s t e r s

........................ ........................

.page 361-362 362-364 364

COOEt

76% 3) Na2S03 T e t r L e t t (1975) 1731

0

RCH 2

I1 -C-OR'

t LOA t Mo05.Py.HMPA

1 ) -70'

2 ) H20

0

II

RCH-COEt

I

OH

Works w i t h l a c t o n e s , ketones JACS (1974)

96 5944

50-80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

362

SECTION 327

1) TiCl

2 EtCOCH-C(0H)COOEt

EtC=CHMe + MeCOCOOEt

I

2) H20

OSiMe3

I 1

87 %

Me Me Chem Lett (1975) 741

PhCHCOCOOEt + MeMgBr

I c1

Et 0

2

OH PhCH-C-COOEt

90%

I t C1 Me

Cornptes Rendus (1974) 279 469

Ro2cm'co

0 II Ph-C-COOMe

H

R

=

(-)-menthy1

n-C6H13CH0 + CH3CHBrCOOEt + Zn -

OH

+

I

Ph-EH-COOMe

82%

21% ee

-

JCS Chem Comm (1976) 101 n-C6H13CHOH-CHCOOEt -

I

73%

CH3

Org React (1975) 2 423

PhCHO

BrCH2COOEt

Zn

*

PhCH(OH)CH2COOEt

continuous f l o w apparatus

JOC (1974) 2 269

97%

SECTION 327

-

ALCOHOL

"Rieke Zn"

PhCHO + BrCH2C02Et

*

ESTER

363

98%

PhCH-CH2C02Et

I

OH S y n t h e s i s (1975) 452

In JOC (1975)

Use o f a c t i v a t e d

40 2253

50-90%

OH H e l v Chim A c t a (1974)

PhCHO

+ MeCH=C'

OTMS

1 ) TiC14, THF, -78" +

2 ) H20

O ' Me

2 1703

PhCH-CHCOOMe

I f

88%

OH Me Chem L e t t (1975) 989

PhCH2CH2CH0

f

CH3C02Et

s-Bu(Me3Si

)2COLi +

PhCH CH CHCH2COOEt

21

77%

OH

T e t r L e t t (1976) 2253 HO

AcOCH2CH2COMe

1 ) LiCH2COOEt -78",

94%

Et20

3 ) KOH, MeOH S y n t h e s i s (1974) 719

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

364

SECTION 328

OH

I

yeast

Ph-C-CH2-C-OEt

Ph-GH-CH2-COOEt

-----+

70%

high optical yie ld Also works with a-ketoesters

Aust J Chem (1976) 29 2459

C-OCH20Me

L DA

HMPA

MeFoH 61 I

C02Me

Me JOC (1976)

5 585

34%

JOC (1976)

Also v i a :

41 1669

Hydroxyacids (Section 313)

Section 328

Alcohol

-

Ether, Epoxide

0

OH

I

94%

OMe

OMe JOC (1975)

40 2976

ALCOHOL - KETONE

SECTION 330 Section 329

b

Alcohol

-

365

Halide

HO CH2C1

CHCl 100%

t

JACS (1974) 96 3010

OH

R-CH=CH2

R

=

H20, Br+

electrolysis

I

R-CH-CH

60%

Br

1" alkyl J Gen Chem USSR (1975)

+

BC13

--+

45 2072

Meo+ \

JCS Chem Comm (1974) 318

Section 330

Alcohol

a-Hydroxyketones. . . 6-Hydroxyketones. . . y-Hydroxyketones. . . Other hydroxyketones.

-

Ketone

..................... .page ....................... . . . . . . . . . . . . . . . . . . . . . . . .......................

366-370 370-373 373-374 374-375

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

366

SECTION 330

OSiMe3 1 ) MCPBA

70%

2 ) H ~ O +o r OH-

T e t r L e t t (1974) 4319

83% U

OH

T e t r a h e d r o n (1976)

0

II R-C-CHN2

H2S04

Ph-C-C-Ph

-

1097

0

II

R-C-CH20H

2.80% Comptes Rendus

vc1

32

C

(1976)

282

1125

0 OH

I1 I

Ph-C-CH-Ph

100%

S y n t h e s i s (1976) 815

Chem L e t t (1976) 95

SECTION 330

ALCOHOL

n-Pr

-

KETONE

367

L i A1 H4

55%

( - )N-methyl e p h e d r i n e 58% e e T e t r L e t t (1976) 3165

OH

Helv Chim Acta (1974)

57

2084

80%

L/

3 ) a l l y 1 bromide

S y n t h e s i s (1976) 341

GMO0,COOMe

Na

~

&

50%

toluene

JACS (1974)

96

5618

368

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

1) MeLi

OAc

H

2 ) ZnC12 +

H

Me

3 ) CH3CH2CH2CH0,

NH4C1

SECTION 330

H

I t CH3CO-C-C-Pr I I

%55%

P h OH

O r g S y n t h (1974)

54 49

OSiMe3 ----t

COOEt

OSiMe? 90%

77%

Org R e a c t (1976)

n

R

"x", .r

(RCHO)

&OH

1 ) BuLi 2 ) R'COR" 3) hydrolysis

R'

23

259

ji

CH ( 0 H ) R ' R"

JOC ( 1 9 7 5 )

5 231

(full paper)

1 ) MeMgBr

75%

2 ) Ht

B u l l SOC Chin1 F r ( 1 9 7 5 ) 3 3 3

SECTION 3 3 0

ALCOHOL

Li 1) CH2=COMe

PhCH2COMe

-

369

KETONE

Me +

I I

PhCH2C-COCH3

2 ) H30t

72%

OH

96 7125

JACS ( 1 9 7 4 )

63%

54 %

JOC ( 1 9 7 6 )

H

OTMS

C3"7

OTMS

C3H7

1) MeLi, Et20

2) E t I

fl 2312

I

C H -C-C-C H 3 7 3 7 Et T e t r L e t t (1974) 3879 T e t r L e t t (1974) 3883

82%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

370

o\

C, H3

$'

SECTION 3 3 0

CH P t anode

85%

TFA, CH2C12

JCS Chem Comm ( 1 9 7 5 ) 262

OH

0

93%

Synthesis ( 1 9 7 6 ) 811

RNC

f

BuLi

-

2"

RN=C,

Li

1) M 2 ) H+

e

A

OH

I

CH3CHCH2COBu

JOC ( 1 9 7 4 )

3

+

PhCHO

90%

39 6 0 0

THF

80%

-80"

JOC ( 1 9 7 4 )

2 3459

1) MeLi TMSO

90%

2 ) CH20, -78"

CH~OH

JACS ( 1 9 7 4 )

96

7114

SECTION 330

ALCOHOL

NOH

-

KETONE

371

n

1 ) Me2CuLi, Et20

90%

2 ) HOAc 3 ) TiC13, NH40Ac

OH

T e t r L e t t (1975) 3117

1 ) Me2CuLi Me2C=CHCOMe

2 ) MeCHO, ZnC12

+

C O M ,e Me CCH \CH(OH)Me

96%

T e t r L e t t (1975) 589

1 ) Me2CuLi ( CH2 ) 3COMe

63%

2) Et20 Me H e l v Chim Acta (1975)

0

Ph-C-C-MgBr

f

0

II CH3-C-COOEt

+

2 ) H30+, Hg(OAc)2

3 1808 Me

I1 I Ph-C-CH2-C-OH I COOEt

55%

S y n t h e s i s (1976) 832

94%

JACS (1974)

96 7503

3 72

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

i-Bu PhCH2CH2CCH3 + Me2CHCH0

(Me3Si )2L!OLi +

i

PhCH2CH2CCH2CHCHMe

I

SECTION 330

71%

OH T e t r L e t t ( 1 9 7 6 ) 1817

1 ) NaH

PhSOCH2COCH3

2) BuLi

3 ) Ph2C0

Ph2C( OH)CH2COCH2SOPh

91 %

T e t r L e t t (1974) 107

R

&

R"

OH

C1 2/PhSMe

80%

o r C12/DMS0 (no C - C bond c l e a v a g e ) T e t r L e t t (1974) 287

42%

T e t r L e t t ( 1 9 7 6 ) 759

SECTION 330

ALCOHOL

-

373

KETONE

73%

NO2

2 400

Angew I n t Ed ( 1 9 7 4 )

a

NO,

Ber ( 1 9 7 5 )

CH20Ac

1924

CH20Ac

hu

+ CH30H

108 1961;

75%

Ph2C0, MeCN

OEt

T e t r L e t t ( 1 9 7 5 ) 297 1 ) LDA

98% OH

T e t r L e t t ( 1 9 7 6 ) 11

Q

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

374

u

2 ) NH4C1

SECTION 330

97%

T e t r Lett ( 1 9 7 6 ) 3105

Bu CBu36-C~CEtl- +

--+

0

70%

---+

OH

Tetrahedron (1974)

30 3037

50%

Chem Comm (1974) 661

+ C5H,,CH0

-

%50%

2 ) H-

3 ) H30+ JACS (1976)

98 2351

SECTION 331

ALCOHOL

-

NITRILE

375

doH 1 ) Ph3CC1, p y r i d i n e

HO

2 ) Ph3C+

JACS (1976)

Also v i a :

79%

BF4-

98 7882

Acyloxyketones ( S e c t i o n 360)

S e c t i o n 331

Alcohol

PhCH2CH2CH2CN

-

Nitrile

1 ) LDA 2) Mo05*Py-HMPA

PhCH CH CHCN

57%

21

OH

JOC (1976)

fl 740

CN

75%

JACS (1974)

Also via:

96

5268

Cyanohydrin t r i m e t h y l s i l y l e t h e r s ( S e c t i o n 366) Cyanohydri n e s t e r s ( S e c t i o n 361 )

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

376 Section 332

Alcohol

A1 lyl ic alcohols.

-

SECTION 332

Olefin

....................... .page ......................

Homoallylic alcohols. . Other olefinic alcohols

......................

376-383 383-384 385

Allylic and benzylic hydroxylation (C=C-CH + C=C-C-OH, etc.) is listed in Section 41 (Alcohols and Phenols from Hydrides)

JOC (1975) 40 2530

85% JOC (1975) 5 1864 Ph

Ph CHO

42% CH20H

Chem L e t t (1976) 581

SECTION 332

ALCOHOL

-

377

OLEFIN

100% T e t r L e t t (1975) 3183

PhSeBr t

(3

cfH++

Na2C03 CF3COO-) 21 ) Agt(

QoH

‘SePH

H20

76% JCS Chem Comm (1974) 100

R‘

I

RC-C-C-CH

‘o/

R”MgBr

R

R” /

CUI

R‘

‘c=c=c’

>go%

‘ CH20H

Rec T r a v Chim (1974)

h-‘

NA1 E t 2

Oo, 3 hr

2 47

R +

HO

90% R

78%

JACS (1974)

96 651 3

378

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION

332

Ho\b

1 ) VO(acac)2-t-EuOH

2 ) Et3N

I

3 ) MsCl

I

A

4

2.30%

&

T e t r L e t t (1976) 2621

H2CH=CMeCH20H

CH2=CH P h L i , -80'

PhCH2CH=CMeCH20H T e t r L e t t (1975) 4419

0-

H

CH2

+ MeCOCH=CHPh

THF

Me

I

98%

HCOCH2C(OH)CH=CHPh Comptes Rendus (1974)

278

533 279 961

SECTION 332

ALCOHOL

-

379

OLEFIN

1 ) PhCHO

Li

2) MCPBA

81 %

Ph HO ' JACS ( 1 9 7 5 )

CH2=CBrCH(OEt)2

1) BuLi

2 ) PhCHO

97

3250

CH2=C-CH(OEt)2

I

PhCHOH T e t r L e t t (1974) 2751 ; 2755

T e t r L e t t (1974) 2215

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

380

p\

Br

+

SECTION 3 3 2

f

2 ) p y r i d i n e , H202 Li

SePh

80% OH

JOC ( 1 9 7 5 )

40 2570

OH

1 ) LOA, THF

PhSe( O)CHCH3

+

I

I

I

2 ) PhCHO 3 ) H+, r f x

CH3

81%

CH2=C-CHPh Me JACS ( 1 9 7 5 )

HC:CCH20H

+ MeCH=CHCH2ZnBr

-3

H2C=C

/

CH

2

97

3250

on

93%

‘-CH-CH=CH~

I

Me Comptes R e n d u s C ( 1 9 7 5 )

280

1473

CH20Li Ph-C:C-CH20H

+

BuLi

-+

L Ph

iU

~

90% P dh C H 2B uO H

A c t a Chem S c a n d

(1976)

30

521

SECTION 332

ALCOHOL

Me2C-C:CCH2CH20H

I

MeMgX -----+

cut

OTHP

-

OLEFIN

381

56%

Me2C=C=CMeCH20H

T e t r L e t t (1975) 1509

EtMgBr

PhC-CCH20H

Cul, E t 2 0

phHEt H

CH20H

J Organometal Chem (1975)

F2C=CFC1

70%

1 ) BuLi, THF, Et20, pentane, -135"

OH

I

PhC-CF=CF2

I

2 ) PhCOMe

91 C1

83%

Me S y n t h e s i s (1975) 122

CH2=CBrCH20H

1 ) L-BuLi 2 ) RCOR'

, Et20

RR'CC(CH~OH)=CH~

I

65-75%

OH

JOC (1975)

40 2975 70%

JOC USSR (1975) 1_1 1691

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

382

2 ) m e t h y l me thane t h i osul fona t e COOMe

3) NaI04 4) phosphate b u f f e r

SECTION 332

A CH OH CH3

%30%

COOMe

T e t r L e t t (1976) 4215

OH PhCH20CH=CH2

BuLi

--.-.-+

TMEDA

I

PhCH-CH=CH,

90%

L

JACS (1974)

96 2576

1 ) NaH

7 5%

2 ) MeOH, (Me0I3P, Me2NH2C1 T e t r L e t t (1976) 2237

8

4=--4=J

OH

50%

Et3N-

Comptes Rendus

C

(1976)

282 391

58%

H e l v Chim A c t a (1975)

58

1094

SECTION 332

Review:

-

ALCOHOL

KETONE

383

Preparation o f a - A l l e n i c Alcohols B u l l SOC Chim F r (1975) 2369

OMe (CH2=CH)2CuLi

72%

Et20, -20" <'

I

0

HO"

2

0

M

e

/

T e t r L e t t (1974) 2439

1 ) i-Bu2AlH EtCzCH

2 ) MeLi

3)

84% I

Et3N

0

S y n t h e s i s (1975) 632

1 ) BuLi MeC-CH

CH2CH20H

62%

____+

2 ) Bu3B

Me

4 ) HOAc Chem L e t t (.1¶75) 397

H2C=CHCH=CH2 + t-BuCu, MgBr2

Me2C0

t-QuCH2CWCH=CH2 -

62%

I

Me2COH

J Organometal Chem (1975)

92 C28

384

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 332

100%

W

S

P

h

Li

60%

dH T e t r L e t t ( 1 9 7 4 ) 2665

PhCH2CH0 + CH2=CH-CH2SiMe3

A 1 C1

PhCH2-CH-CH2CH=CH

CH2C12

I

OH T e t r L e t t (1976) 2449

97%

JOC (1976)

1 ) Me3SiCH2K, p e n t a n e

41 550

s""' S y n t h e s i s (1975) 328

83%

SECTION 335

-

ALDEHYDE

OCH2CH=CH2

I

I

2 ) H20

38 5

OH

OTMS 1 ) TiC14, MeC=NPh

AMINE

CH2CH=CH2

P

&if

Chem L e t t (1975) 1041

Also via:

Acetylenes

S e c t i o n 333

Aldehyde

-

A l c o h o l s ( S e c t i o n 302)

-

Aldehyde

-

Amide

-

Amine

No a d d i t i o n a l examples

S e c t i o n 334

Aldehyde

No a d d i t i o n a l examples

S e c t i o n 335

Aldehyde

No a d d i t i o n a l examples

88%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

386 Section 336

Aldehyde

-

Ester

1 ) (~--Bu)~NH

n-C H CH CHO - 3 7 2

’

2) BrCH2COOEt

70%

n-C H CHCHO

-

71

CH2COOEt

3 ) H30f

Synth Comm (1974)

NOCl,

EtOH

CQOEt

’

95%

CH=NOH.HCl JACS (1975)

Also v i a :

Section 337

5 147

C

so2

SECTION 337

97

3848

Carboxyaldehydes ( S e c t i o n 314)

Aldehyde

-

Ether, Epoxide

1 ) (i-PrO)4Ti, PhCH2CH2CH0 + CH2=CHOEt

2 ) EtOH

TiC14 +

100%

0-1-Pr Chem L e t t (1975) 569

SECTION 339

-

ALDEHYOE

KETONE

387

Br2, -78'

-70%

NaOMe, MeOH

Q7B(OH)z

/ Br

CH-CH(OMe)2

JOC (1975)

-

N-t-BU II P~--cH~-?H

11 NBS

2 ) H30S

40 1189

58%

Pr-CBr2-CHO S y n t h e s i s (1975) 455

S e c t i o n 339

Aldehyde

-

Ketone

T e t r L e t t (1974) 3253

*G 0

\Ono / PhS02CH2CH2CH

1 ) BuLi 2) 3) A1-Hg

COOMe

T e t r L e t t (1975) 1397

%70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

388 Section 340

Aldehyde

-

SECTION 341

Nitrile

66% Synth Comm (1974)

I OH

4 331

II

pyridine/THF

85%

NC-(CH2)4CH0

Synthesis (1975) 665

Section 341

Aldehyde

-

Olefin

.....................

a B - o l e f i n i c aldehydes. Other o l e f i n i c aldehydes

......................

.page 388-394 394-395

F o r the o x i d a t i o n o f a l l y l i c a l c o h o l s t o o l e f i n i c aldehydes see Section 48, Vol. 1 (Aldehydes f r o m A l c o h o l s )

58%

JCS P e r k i n I (1974) 37

SECTION 341

ALDEHYDE

-

OLEFIN

389

1 ) Ph3P

2) L i m e

,,cH2
C6H1 3CH=CH-CH0

96%

3 ) C6H13CH0 4 ) H+ JCS P e r k i n I (1974) 37

56%

Angew I n t Ed (1975)

Me I

1 ) Me SiC-C=N-t-Bu I 1 Li H 2 ) o x a l i c a c i d , HpO

’

14 1486

M?5Ho

90%

T e t r L e t t (1976) 7

67%

n

O,\ PhS02C-CH2-CH

I

(CH2)7Me

JOC (1975)

1 ) aq H O A ~ *

2 ) base

40 3313

Me(CH2)7CH=CH-CH0

T e t r L e t t (1975) 1007

85%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

390

1 ) BuLi

CH3CH2F

Is] cS Me E t Me

CH C=C-C

31

2 ) Me1

Et

SECTION 341

87%

I

T e t r L e t t (1974) 3171

MeCH=CH-CH( OMe)* + CH2=CHCH=CHOSiMe3

1 ) TiC14, THF

2 ) H20

86%

MeCH=CHCH(OMe)CH2CH=CHCH0

CH3N02

piperdine

6

HO

C5H5NHCr03C1 CH2C12

’

Chem L e t t (1975) 319

55% S y n t h e s i s ( 1 9 7 4 ) 196

&

85%

(mixture o f E and Z )

S y n t h Comrn ( 1 9 7 6 )

5 469

SECTION 341

ALDEHYDE

-

OLEFIN

391

several steps OH

Org Synth (197

54 -

9

RCH=CHCH(OEt j 2

1 ) RMgBr/ HC-C-CH ( O E t ) 2

/2)

\l)

R = Ph,

H*0 RMgBr

L-Bu, E-BU, c y c l o p e n t y l Rec T r a v Chim (1976)

95 66

A 1 , 3 - a l k y l a t i v e c a r b o n y l t r a n s p o s i t i o n , e.g. :

1 ) CH2=CHMgBr

44%

3 ) PhSSPh JACS (1975)

2 4018

COMPENDIUM

392

OF ORGANIC SYNTHETIC METHODS VOL 3

1 ) CH2=CHOEt, Hg(OAc)2

'

2 ) 225O, 5 h r s

HO'

SECTION 341

&?i

50%

C,,CHO Org Synth (1974)

Me0

54 71

CHO

68%

S y n t h Comm ( 1 9 7 6 )

NNHTs

1 ) BuLi 2 ) DMF 3 ) H20

'

5

119

DCH0

54%

T e t r L e t t ( 1 9 7 6 ) 2287

80%

Rec T r a v Chim ( 1 9 7 6 )

95 308

r

SECTION 341

-

ALDEHYDE

(Ph3SiO)3V0 -t

150"

OLEFIN

393

%go%

"'CHO

OH

t-BuOCH2CH'CHZ

1) E - B u L i +

2 ) MeSSMe

Helv Chim Acta (1976)

59

1233

72%

t-BUOCHCH=CH2 -

1

SMe JACS (1974)

96 5560 94%

T e t r L e t t (1976) 2313

0

0

PhCOCH3 +

It HC-CH=N-NHPh

1) EtOK, EtOH 2) hydrolysis

+

II

%80%

PhCOCH=CH-C-H

Chem Ber (1975)

108 8 8 ;

1756

OMe

PhCHO

+

Fh+CHO

76% OMe Synth Comm (1976)

6

119

COMPENDIUM OF ORGANlC SYNTHETIC METHODS VOL 3

394

Ph3P=CHCH0

OHC-CHO

OHC- ( C H = C H ) ~ C H O

DMF, 80"

77%

Chem B e r ( 1 9 7 4 )

1) F M g B r HO

SECTION 341

107 7 1 0

CH3CH2

2 ) DMSO, B F 3 * E t 2 0

+=/

CHO Chem L e t t ( 1 9 7 6 ) 1 2 9 7

PhCHCH2CH=CHCH0

I

OEt

DBU

PhCHZCH-CHZCHCHO

-----+

CH,CL1

79%

L

Chem L e t t ( 1 9 7 5 ) 1 1 6 7

94%

35% JCS Chem Comm ( 1 9 7 5 ) 206

95%

4 ) H30t

T e t r L e t t (1975) 3685

AMIDE

SECTION 343

-

39 5

AMINE

75%

OHC\ COOMe I

Me Can J Chem (1976)

A l s o via:

3 3304

6-Hydroxyaldehydes (Section 324)

Section 342

Amide

-

Amide

61 %

Also via:

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) Diamines ( S e c t i o n 350)

Section 343

Amide

-

No a d d i t i o n a l examples

Amine

COMPENDIUM

396 S e c t i o n 344

Amide

-

OF ORGANIC SYNTHETIC METHODS VOL 3

Ester

SECTION 344

0) Et

(Et)*CuLi

+

------+

C1 COOCH3

N

I

Et20

COOCH3

Can J Chem (1975)

C1 3CCH=NCOOEt + MeMgX

Et,DL

52 3563 56%

C1 3CCHNHCOOEt

I

Me JCS P e r k i n I (1975) 2511

CH3CH2(CH2)n--COOR

+ e-

---CHJCN

40-70%

CH3CH-(CHz)nCOOR

I

NHCOCH3

E l e c t r o l y t i c W-1 o x i d a t i o n JOC (1974)

2 369

53%

COOEt Chem Ber 11975)

500

-

AMIDE

SECTION 345

EPOXIDE

397

R

47-70%

I

R

R = a1 k y l , b e n z y l JOC (1975)

Ph-NCO

t

Sn o c t a n o a t e p

Me2C-OH

+

I

40 1505

Ph-N-C-O-CMe2

Can J Chern (1976)

S e c t i o n 345

Amide

-

No a d d i t i o n a l examples

Epoxide

90%

54

24

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

398

Section 346

Amide

-

SECTION 347

Halide

c1

69%

JOC (1975)

9 1287

0

0

d i bromoisocyanuric a c i d

II

CH3-C- NH2

r

(DBI)

II

Monatshefte (1975)

S e c t i o n 347

Amide

106 611

- Ketone

1 ) PC15

I COCH3

83%

CH3-C-NHBr

2 ) (cooEt)z

4

45%

N

I

c=o I

~H,COCOOH E x p e r i e n t i a (1976)

4

'NF-CH,

32

1491

vH3

ObT-CH, P t anode

CH3CN, H20

f

JCS Chem Comm (1975) 262

70%

SECTION 348

Also via:

AMIDE

-

399

NITRILE

K e t o a c i d s ( S e c t i o n 320)

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

-

Olefin

60-70% L i e b i g s Ann Chem (1974) 1655

75%

JACS (1974)

96 5563

OMe

65%

Org Synth (1974)

54 77

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

400

H

R

X,,.

t HC-CCOOR'

t

CH2=CH-COOMe

COOEt

PhC=N-Ph

1

-

AXR

SECTION 349

COOEt

60-85%

0

T e t r L e t t (1974)

3 623

A1 C1

85%

CH3 T e t r L e t t (1974) 977

5 r

NHNH?

0

0 Li2PdC14

E t 3 N , MeCN

,

A$

402

H Chem and I n d ( 1 9 7 6 ) 1032

81 %

COOMe S y n t h e s i s (1975) 643

Also v i a :

O l e f i n i c a c i d s ( S e c t i o n 322)

AMINE

S E C T I O N 351

S e c t i o n 350

Amine

-

-

ESTER

401

Amine

~70%

NHPh S y n t h e s i s (1974) 504

57%

PPh

Bz -

WNHB JOC (1975)

OMS

I

Ph-CHCH20MS

40 558

H2NNH2 ____+

Ph Org Synth (1976)

S e c t i o n 351

Amine

-

55

114

Ester

D i r e c t e s t e r i f i c a t i o n o f aminoacids and aminoacid h a l i d e s . o f e s t e r s o f aminoacids. E s t e r s o f aminoalcohols.

Other preparations

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

402

Bz

2 ) LDA NH2CH2CO2-L- BU

3 ) BzBr

4 ) H30t

SECTION 351

+

I

H2NCHCO2-t-B~

7 9%

0 72% ee JCS Chem Comm (1976) 136

COOMe

N-BOC

I

1 ) -0Me

COOMe

*60%

2 ) HC1

3 ) NH3

NH2

c1 Angew I n t Ed (1976)

15 294

COOEt

MeCXNEt2 + CH =C

c,1 ‘COOMe

= c’h Et2N

89%

Me

T e t r a h e d r o n (1974) 30 3481 T e t r L e t t (1974) 1 4 w w i t h cyclohexenone

84%

Chem Comm (1974) 587

AMINE

SECTION 351

-

ESTER

403

R'

H' +

R~ C O C H ~ - C H C O O H

I

HO-CH-COOH

I

NHCOPh

NHCOPh

+ R' CO k N0 H C O P h

CHCOOH R2C0 R's

RCHO

=

NHCOPh

Me, Ph, OMe

+ CNCH2COOR'

J C S Chem Comm (1975) 905

-

COOR'

DBN

THF

50-71% 6 C O O R ' H JOC (1974)

2 1980

R ' OCH=NR

rn

N v N H

+

RNC

AgCl

65%

90% N- R

w COOEt )

( EtOOC)2CHCHNHR T e t r L e t t ( 1 9 7 4 ) 1283

80%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

404

Me T C O O E t

SECTION 352

POCl __3

89%

Angew I n t Ed (1976)

15 498

a::2Et /

Et

QEt

I

Me

Me

NHCOOEt

JOC (1976)

S e c t i o n 352

Amine

t

83%

2 195

Ether

Me SiCrCSiMe + Mes-CEN-03 3

Chem B e r (1974)

707 3717

65%

T e t r L e t t ( 1 9 7 4 ) 1531

AMINE

SECTION 354

S e c t i o n 353

0

Arnine

-

-

KETONE

405

Halide

0

II

1 ) (Et0)2PNBr2, BF3.Et20

,~2) NaHS03

'NH2 -HC7

3 ) HC1

Angew I n t Ed (1976)

15 302

74% (t6% ortho) Br JOC (1975)

ArNH2

c1

2o

40 1867

ArNHCl A u s t J Chern (1976)

S e c t i o n 354

Amine

-

+

367

Ketone

Me2k=CH2 CF3COORCOMe +

29

-i - P r2 N=CH2C104

T FA

CH3CN

I

Me2NCH2C-COMe

I

\

,CHCOCH2CH2NR2 JCS Chem Comm (1974) 253

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

406

il

PhCCH=CHPh

PhN=S=O ____+

SECTION 354

0

11

PhCCH2CHPh

I

cu

NHPh

JOC (1976)

93811

+

1 ) H2C=NMe2 -C1 Ph

CHMe2

78%

2 ) OHtH2NMe2 Angew I n t Ed (1976)

239

T e t r L e t t (1974) 3963

COCH3

COCH3

I

CH30H, H2C0

+NO2OH

W2 Raney N i c k e l

’

~70% P N M e ,

OH I n d i a n J Chem (1975)

H

RCCOOR’

I

NH2

+ p-N02C6H5N2

DMF Et3N

13 33

0 R 8 0 Y 2 R JCS Chem Comm (1974) 558

40-90%

SECTION 356

AMINE

-

OLEFIN

t

N2

R4N X

CH3COCH2COCH3 t tosN3

407

+

two phase system

II

CH3COC-COCH3

80%

S y n t h e s i s (1974) 347 T e t r L e t t (1974) 1391 f o r polymer bound TsN3

S e c t i o n 355

Amine

-

Nitrile

CN

I

1 ) Me3SiCN, Zn12

PhCH=NCH2Ph

PhCH

+

I

2 ) H20

98%

NHCH2Ph Chem L e t t (1975) 331

-

83%

NC(CH~)~CN

KH, THF

CN

S y n t h e s i s (1975) 326

S e c t i o n 356

Q

I CHO

Amine

-

Olefin

OMeH

I

CHO S y n t h e s i s (1976) 545

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

408

SECTION 356

0 KH, Me1

-50%

hN3

Me Synthesis (1976) 401

0

II

Me-C-CH-CN

I

ArNH2

Me-C=C-CN

60%

I

I t A r N H C1

c1

Chem Ber (1976)

0

II R-C-CHC1-CHO

HNR'2

109 2908

0

I1

R-C-CC1=CHNR'2

35-48%

R = Ph, OEt R I 2 = Me2, E t 2 ,

(CH2I5 Comptes Rendus

PhNCH2CH=CH2

I Me

1 ) BuLi ___I)_

5 (1976) 282 935

PhN-CH=CHCH3

2 ) Me1

I Me

S y n t h e s i s (1 974) 672

benzene

Ts T e t r L e t t (1976) 3919

75%

qH Q” SECTION 356

AMINE

NH4Br

-

OLFEIN

409

~

66%

COOEt

JCS Chem Comm (1975) 682

PrCH PhCN

f

PrCH2Li

II

1 ) PhCN ___+

2 ) H30t

Ph’

63%

C-NH

I C=NH I Ph

T e t r L e t t ( 1 9 7 6 ) 147

yvEuHZN ‘Me

Na[Et3BCTC-CH3]

t

+ CMe2NCH21Br2)

xEv 1 ) E t A1

CH2NMe2

Chem B e r (1975)

108 395

H

51 %

T e t r L e t t ( 1 9 7 6 ) 757

410

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 356

c1 R

-0 I

I

130"

t

60-73%

I

0

JACS (1976)

98 2901

94%

Comptes Rendus

Me2NCH2CKCH2NMe2 + EtMgBr

C

(1976)

282

1003

-

7 3% Et J Organometal Chem (1975)

+ Me2C=C=CMe2

S 297

-@

100%

HoAc

I n d i a n J Chem (1975)

13 1124

SECTION 356

AMINE

-

OLEFIN

41 1

96%

JOC ( 1 9 7 4 )

Q NH2

39 781

1 ) J-BuOCl 2

85%

MeSCHCOCH3

I

CH3

H

3) Et3N

4 ) LiA1H4 JCS Chem Comm (1974) 201

1 ) ROC1 2 ) CH3SCH2COCH3

3 ) Et3N

H __t

Ra N i JACS (1974)

96 5495

96 5508 (oxindole)

'ji; 5512

75%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

41 2

Section 357

C1

Ester

f

-

SECTION 358

Ester

(- 1 CH(COOEt)2

-

----

CH( C O O E t I2

50-90%

Cr( CO 1

JACS (1974)

Me2CHC02Et

1 ) LOA, THF 2) 12, THF

*

96 7091

Me2CCOOEt

85%

I

Me,C-COOEt L

Synthesis (1975) 396 Chem L e t t (1975) 621 ( e l e c t r o l y t i c coup1 i n g )

'Also via:

Section 358

O 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) Diols (Section 3 2 3 )

Ester

-

Ether, Epoxide

42%

Angew I n t Ed (1976)

15 436

SECTION 359

ESTER

0

II

PhCHO + BrCHpC-S-t-Bu

-

- /I It NaH

PhCH

DMF

C-S-t-Bu

67%

0

JOC (1974)

S e c t i o n 359

41 3

HALIDE

39 2938

Ester - Halide

100% Chem Pharm B u l l (1976)

24

820

76%

S y n t h e s i s (1976) 121

b

+

CHBr2CN

i-PrOH

i- P r O K

74%

QBr

COOL-Pr Comptes Rendus (1974)

278

77

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

41 4

Me

I

Me-CH=C-COOMe

1) EtjSiH,

I

92%

Me-CH2-C=C( C1 )COOMe

+

Chem Pharm Bull (1976)

N-iodosuccinimide

SECTION 359

Me

Rh(1)

2) PhHgCBrC12

VOL 3

24

+

1957

70-95%

RCOOH, CHC13

I1

R

=

0

Me, A r , CF3. H

T e t r L e t t (1976) 3661

>=(

t T1

0 OC-R II

f

I2

-

I I

i

I-C-C-OC-R

I I

high y i e l d JCS P e r k i n I (1974) 1858 JCS P e r k i n I (1974) 1864 (Iodolactonization)

RCH- ( cti2),CH20H

I

t PhgPBr2

OH

DM F

-20"

RCH- (CH2 ),-CH2Br

I

OCHO

D i f f e r e n t i a t i o n between O H ' S i n d i o l s 1"

+

2"

+

Br forrnate e s t e r T e t r L e t t (1974) 913

50-90%

ESTER

SECTION 360

-

415

KETONE

52%

JOC (1975)

Also v i a :

40 2843

Haloacids ( S e c t i o n 319) Halohydrins (Section 329)

Section 360

Ester

-

Ketone

.page Esters o f a-ketoacids. . . . . . . . . . . . . . . . . . . . . . Esters o f 6-ketoacids. . . . . . . . . . . . . . . . . . . . . . . . E s t e r s o f y-ketoacids. . . . . . . . . . . . . . . . . . . . . . . . E s t e r s o f 6-ketoacids. . . . . . . . . . . . . . . . . . . . . . . . Esters o f o t h e r ketoacids. . . . . . . . . . . . . . . . . . . . . . Acyloxyketones . . . . . . . . . . . . . . . . . . . . . . . . . . .

RCOCH2COR1

41 5 415-418 418-419 418-420 421 421

Se02 or 1 ) Br2/Py

------+

2 ) DMSO

70%

RCOCOCOR'

Helv Chim Acta (1974) 0 MgBr

I1 I Ph-!-bH-COOEt

\CHO

2) A

57 2201

90% 0

T e t r L e t t (1975) 2841

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

41 6

&-

COOE t

- OH ,

-

pha s e t r a n s f e r ca t .

COOEt

'

BzBr

&Bz

SECTION 360

95%

Chem L e t t ( 1 9 7 6 ) 1259

87%

JOC USSR ( 1 9 7 5 )

COOH

1 ) Mg( OMe)OC02Me 2 ) MeOH, Hf

11 2360

92%

Me02C

-+

0 JOC ( 1 9 7 4 )

2 3144

n 85%

OH T e t r L e t t (1975) 2389

& 0

0

C02Me

PhH

C02Me

r

CH2=CHCH2Br R3NMetC1 -

85%

I

CH2CH=CH2 JOC ( 1 9 7 4 )

39

3271

SECTION 360

ESTER - KETONE

JACS (1975)

417

2 3822

74%

Angew I n t Ed (1974)

0

13 77

0

90%

Synth Comm (1976)

6

429

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

418

BF3-Et20

N2CHCOOEt

SECTION 360

-tf COOEt

+

96%

Synth Comm (1975) 5 125

Et02C(CH2)4COOEt

-

COOEt

KH, THF

95% Synthesis (1 975) 326

I C

I

H

EtO

OEt 73%

115" Tetr Lett (1976) 341 0

83%

Bull Chem SOC Japan (1976) 49 1055 COOMe

( EtC0)20

COOMe

ZnCl

Bull SOC Chim Fr (1975) 274

55%

SECTION 360

ESTER

-

KETONE

419

COOMe JACS (1974) 96 8102 JOC (1974) E l 8 7 3

0 - Na'

&

COOEt

C02Me T e t r L e t t (1975) 4531

0

93%

T e t r L e t t ( 1 9 7 5 ) 3841

420

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 360

70-98%

R's

=

alkyl, Ph Chem L e t t ( 1 9 7 6 ) 1 6 3

50%

S y n t h e s i s (1976) 110

0

0

1 ) LDA, THF/HMPA,.-60"

70%

2 ) MeCH=C(SPh)COOEt CbOEt

Bull Chem Soc J a p a n (1975)

93 7 6 9

6-

SECTION 360

ESTER

CH2=CH(CH2)3COOMe +

-

KETONE

ROOR

421

&(CH2)5COOMe

C o l l Czech (1976)

7 0%

41 1698

OCOPh

1) lead tetrabenzoate

+ &

2 ) Et3NHF

JOC (1976)

xe3

91 %

5 1673

B u l l Soc Chim France (1976) 642

1 ) Pb(OAc)q

Ph

CH2

2 ) H30t

'

95%

Ph Synth Comm (1976)

R

PhCHOCPh

+ MeCHO

K2C03

t-BUOH -

6 59

59%

PhCOCHMe

I

OC-Ph

I1

0 T e t r L e t t (1975) 903

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

422

Also v i a :

SECTION 361

K e t o a c i d s ( S e c t i o n 320) Hydroxyketones ( S e c t i o n 330)

S e c t i o n 361

Ester

-

Nitrile

a, B and h i g h e r c y a n o e s t e r s .

Esters o f cyanohydrins

CN

CN

Me C-C'

I

1 ) EtMgBr 2 ) H30C

'COOEt

Me2C-CHCOOEt

62%

I

'

Et Angew I n t Ed (1975)

L i C l , HMPA

NCCH2COOEt + PhCH2Br

14 629

NCCH(CH2Ph)COOEt + NCC(CH2Ph)2COOEt

160"

30%

64%

Chem L e t t (1975) 1149

COOEt

I MeCHN-C

1)

COOEt

I

L-BuOK +

2 ) PhCH2Br

Me-C-NX

7 9%

I CH2Ph Chem B e r (1975)

0

II

(CH,C-)20

+ Ph3P=CHCOOEt

HCN

Me)=(H NC

108 1580

58%

COOEt

cis- trans mixture C o l l Czech (1976)

41 2040

SECTION 362

ESTER

-

OLEFIN

423

+

1 ) E t 4 N NCC02-

CH NC3'

85%

2 ) Me1

JCS Perkin I (1976) 1926

75% COOEt

Org Synth (1976)

Also via:

Section 362

55 57

Cyanoacids (Section 321) Hydroxynitriles (Section 331)

Ester

-

Olefin

a,B-Olefinic e s t e r s . . B,y-Olefinic e s t e r s . . y,&-Olefinic e s t e r s . . Other o l e f i n i c e s t e r s . Enol e s t e r s . . . . . .

.

. , . .

. . . . .

.... .... .... . . . . . . . .

. . . . . . . . . . . . . . . .page ................. .............,... ........ ...... ... .,........ ...... .

423-476 437 438 438-439 439-440

For a l l y l i c acetoxylation see section 116, Vol. 1 and 2 (Esters from Hydrides)

Review: "Methods for the Synthesis o f a-Methylene Lactones" Synthesis (1975) 67 Review: "Synthesis of a-Methylene-y-Butyrolactones" Synth Comm (1975)

5 245

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

424

SECTION 362

72%

T e t r L e t t (1974) 1100 JCS Chem Comm (1974) 135

50%

T e t r L e t t (1974) 339 Synth Comm (1974) ff 133

+ PhCHO

PhH

J3

100%

0

Ph

JOC (1974)

i+

2 3236

paraformaldehyde PPh3

0

THF 0 JOC (1974)

39

1958

SECTION 362

ESTER

-

OLEFIN

425

-50%

U

3 ) CF3COOH

T e t r L e t t ( 1 9 7 5 ) 4099

PdC12 'C-CH H2N-C-NH2,

Me2C0

t

o<,po

62%

CH2 JCS Chem Comm ( 1 9 7 6 ) 9 0 7

60-80%

J C S Chem Comm ( 1 9 7 5 ) 887

JACS ( 1 9 7 5 )

97

7182

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

426

9 0

1) i-Pr2NLi

2) CH31

3 ) i--Pr2NLi

+

4 ) PhZSe2 5 ) H202

9

40%

0

JOC ( 1 9 7 4 )

39 121

Chem 6 e r ( 1 9 7 4 )

OHc$o

NaCNBH3

I I _ +

Me2NH

SECTION 362

X'O Me1

H2$0

52%

NaHC03

JOC ( 1 9 7 5 )

COOEt

107 2853

40 3474

COOEt

1) LDA

SPh

2 ) PhSSPh

1) oxidation

>

2) A 76%

COOEt

JACS (1976)

98 4887

SECTION 362

TMSCHCOOEt

I

+

Li

e

COOEt

ESTER

-

-

OLEFIN

427

6'"

95%

JACS (1974) 96 1620 T e t r L e t t (1974) 1403

R COOEt

1 ) NaH-THF

+ R'

50-90%

COOEt

JACS ( 1 9 7 4 )

PhCHO +

96 1607

------+

60%

Ph H

3

Z Chem ( 97

62%

JACS (1974)

96 1082

bo

c1 HOCH2C-CH

1 ) HgC12, H$J

2 ) CO, Li2PdC14

+

T e t r L e t t (1976) 4661

96%

428

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

VOL 3

SECTION 362

COOEt

1 ) base 2 ) PhSex 3 ) H202 JOC (1974)

4

39 2135 39 120

T e t r L e t t (1974) 2279

PhSeGcooMe

1 ) PhSeH

+

2) BuLi

H202

-

COOMe

~50%

3 ) CH30COC1

T e t r L e t t (1976) 453

95% Bull Chem SOC J a p (1974)

65s

47

2529

CHCOOE t

It

Et0-C-S-CH2COOEt S

+

Chem L e t t (1976) 917

78%

SECTION 362

ESTER

-

429

OLEFIN

CH20Li Ph-C-C-CH20H

+ BuLi

77%

-+

Ph

Bu Ph

Lk A c t a Chem Scand

(1976)

Bu

30

521

CH2Br +

I

BrCH2-CHCOOH

---+

NaoH DM F

YOOH

37%

S y n t h e s i s (1975) 599

\

Ph 70%

Chem L e t t ( 1 9 7 5 ) 939

PhCH COO-K+ + Ph2C-CHO 2

I

Br

1 ) 18-crown-6 90%

2) A

JOC (1975)

40

3139

4 30

P-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

'*A

Ph

COOH

SECTION 362

lithium chloropalladite H20

0

Me

67%

Me

B u l l Chem SOC Japan (1975)

48 1673

B u l l SOC C h im France (1975) 751

Can J Chem (1975)

2

195

80%

Ph-CZC-CHO t PhCH2COOH --+ Ph

T e t r L e t t (1975) 1457

kcooMe OCOMe

1 ) Me2CuLi 2 ) C1 COOMe

46%

*

Me

JOC ( 1 9 7 5 )

40 1488

SECTION 362

ESTER

-

431

OLEFIN

72%

T e t r L e t t (1975) 1621

b

COOMe COOMe

COOMe 95%

COOMe

JCS Chem Comm (1974) 384

JACS (1974)

Me3SiCHzCOOEt

1 ) (cyclohex)2NLi

96 6153

R >CHCOOEt R'

R' JACS ( 1 974)

96 1620

1 ) LDA TMSCHZCO2$-B~

2 ) PhCHO 3) H30t

PhCH=CHCOOtBU T e t r L e t t (1974) 1403

75%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VDL 3

432

(Et0)2POCHC02Et + PhCOCH3

I

base

Ph

Me

‘c=c’

Me’

SECTION 362

65%

‘COOEt

S y n t h e s i s ( 1 9 7 4 ) 122 (1974) 869 T e t r L e t t (1974) 711

Me

I

n-C5H11CH=CH-C=CHC02Me

68%

!-C5H1

74%

Cd I D B y a

n-C5H1 ,CHO + Ph3PCH2C=CHCOOMe t r ’ -

1 \7 i-Pr2NEt . ‘-,

CH=C-COOMe

1

MeC=CH2 JOC (1974)

BrCH2C02Et +

PhS02

I

--+

39 821

98%

+

ethanol C02Et

B u l l SOC Chim France ( 1 9 7 6 ) 525

1 ) DIBAL-H

t-Bu-CECH

2) CiCOOEt

t-BU

72%

3 ) H30t

COOE t S y n t h e s i s (1976) 625

ESTER

SECTION 362

-

433

OLEFIN

Et&

7 0% COOEt

Et

HC-CCOH + k B ( "

COOEt

76%

COOEt

Et

JOC ( 1 9 7 4 ) 2 2321

T e t r a h e d r o n (1974)

30 835

FOOEt 70%

JACS ( 1 9 7 4 )

(EtCO)+I + BrZnCHCOOEt

I

Me

--+

96 7138 76%

EtC=CMeCOOEt

I

OCOEt

JOC (USSR) ( 1 9 7 5 )

fl 2360

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

434

OL i

CH2=CHCH3

+ PhSOCH=COCH3 I

(Pd<>

---+

SECTION 362

---+R3P

40-90% -COOMe JACS ( 1 9 7 4 ) 96 7 1 6 5 JOC (1974) E 7 3 7

1 ) HMPA, 25"

+ PhSOcHCODMe

'2'

2

cuclh

86 %

2 ) a00

JACS ( 1 9 7 4 )

96 7165

JACS ( 1 9 7 4 )

3

C , '

COOMe

\

COOMe 7349

/ CN

CH

gCOoEt THF,

rfx

64% NC

COOEt S y n t h Cornm ( 1 9 7 6 )

MeCH=C'

NMePh

'COOMe

1 ) J-Pr2NLi

2) Me1

+

MeCH2CH=C

6

185

,NMePh 'COOMe

S y n t h e s i s ( 1 9 7 5 ) 512

80%

SECTION 362 PhTl ( TFA)2

ESTER

+ HC-CCOOMe

-

OLEFIN PhCH=CHCOOMe

+

L i 2PdC1

435

88%

CuC12, MeOH

J Organometal Chem (1975)

//\/PPh3

t

1 ) LDA 2 ) CH=CHCOOMe

’

98 C8

PhCH=CHCH=CH-CH=CHCOOEt

84%

I

c1 3 ) PhCHO

T e t r L e t t (1975) 1359

Ph

H 72%

80%

23 229 Chem Pharm B u l l (1975) -

CH2(COMe)2 + t-BuNC

cu 0

2 PhH

(MeOC)pC=CHNt-Bu

34%

J Organornetal Chem (1975)

PhCH=CHHgCl

CO, MeOH -----+

PdCl

PhCH=CHCOOMe JOC (1975)

85 395

100%

40 3237

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

436

OAc

SECTION 362

0

U

M 18:l Z t o

E

e

AcO

1:15 Z t o E T e t r L e t t (1974) 925

EtCOOH + HgOAc2 + v i n y l v e r s a t e 10

H+

EtCOOCHCH2

Tetrahedron (1974)

30 4205

0 0

(1

Bu2CuLi

MeCsCSEt

____+

THF -780

Me

II 100%

)=/'\Et

BU JOC (1974)

@:

+ Ph3;-ctiCOEt

2 3174

-

60%

0

EtOC

H

II

0

A u s t J Chem ( 1 9 7 5 )

28 2499

SECTION 362

ESTER

- OLEFIN

431

70%

COOH

72%

JACS (1915) 97 6892

Comptes Rendus

MeCH=CHCHpZnBr + C1C02Et

Et"0

-1 5"

(1915) 280 999

MeCH=CHCH2COOEt

10%

J Organometal Chem (1915) 96 163

80%

'CH~COOM~ JOC (1974) 39 2631

438

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 362

2.50%

kH2COOMe T e t r L e t t (1976) 495

~50%

Org Synth (1974)

O

54 74

c e r i c ammonium n i t r a t e

65% M e, , , \

Chem and I n d (1976) 565

21 ) HgOAc NaBH4, NaOH

~

$\-,.DAC

57%

3 ) Ac20, p y r i d i n e S t e r o i d s (1976) 27 197

ESTER

SECTION 362

-

OLEFIN

439

41 ) (CH2=CH)2CuLi

65%

2) TMSCl 3) o3 4) NaBH,

Tetr Lett (1974) 1713 COOMe C

tetralin

15%

rfx

COOMe Angew

COOMe Int Ed (1976) 15 104

62%

JACS (1975) 97 5873

440

OMe

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

OMe

SECTION 362

7 JCS P e r k i n I (1976) 1438

MeC:CCH20H

1 ) CH2=CHCH2MgC1

75%

2 ) Ac20, p y r i d i n e

CH20Ac Synth Comm (1976)

6 319

95%

Angew I n t Ed (1975)

Also via:

A c e t y l e n i c e s t e r s ( S e c t i o n 306) O l e f i n i c a c i d s ( S e c t i o n 322) B-Hydroxyesters ( S e c t i o n 327)

14 636

ETHER - HALIDE

SECTION 364 Section 363

Ether

- Ether

Li, Me3SiC1

Me ( CH2)4CH0

441

DME

OTMS

I

Me(CH ) CH-CH-(CH2)qMe 2 41 OTMS

60%

Synthesis (1975) 787 CH,

CH, CH30H

71 %

electrolysis Synthesis (1975) 717

Section 364

EtO/==

+

Ether - Halide

CuC12 + K I + MeOH

--+

I

moderate yield

Bull Chem SOC Jap (1974) 47 2818

iC,HCO@-@ Tetr Lett (1975) 4637

442

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 365

55%

JCS Chem Comm (1974) 196

4-+ 4' Section 365

Ether, Epoxide

-

Ketone

1 ) LDA

+

P

S

M

e

2 ) MeSSMe

1 ) Hg++, MeOH

c

2 ) CuC12, H20/THF

I n d i v i d u a l y i e l d s >90% T e t r L e t t (1976) 4687

98%

PhCH-OSiMe3

I

CN

Synthesis (1975) 391

SECTION 365

ETHER, EPOXIDE

RCXCH(OEt)2 +2RI2BH

-

- E NaOH/H20

RCH2 CH20Et JACS (1974)

Me C CH=CHCOMe

I-

CH20Ts

443

KETONE

MeO-

2

316

f f

COMe OMe

Chem B e r (1974)

107 887

F=CH CH CNO

Ra N i

3

HOAc

74%

J Gen Chem USSR (1975)

5 2534

.\.loo% N02 0

0 T e t r L e t t (1976) 719

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

444

SECTION 367

84% Synthesis (1976) 532

Section 366

Ether, Epoxide

- Nitrile CN

‘COOEt JCS Chem Comm (1975) 95

Me’Y OEt

ClCH CH CHCN

21

I

NaN (TMS )2 95”

OCHMe

’

bEt

Section 367

62%

Tetr Lett (1975) 389

Ether

0 11 2 + Et03CH R’CCH2R

- Olefin Amberlyst 15 cat

+

OEt 1 2 R’-C=CHR Synthesis (1974) 348

70-100%

ETHER

SECTION 367

PhCH2C1

1 ) Ph3P

-

OLEFIN

Ph

------+

90%

-0Et

2 ) HCOOEt

JOC (1976)

+

445

+

PhOH + Ph3P-CH=CH-PPh3 (2Br-)

1) Et3N 2 ) NaOH/H20

41 1272

Ph-O-CH=CH2

+

76%

Synthesis (1975) 736

CH2=CH-CH20THP

1 ) A-BuOK sec-BuLi -

t

‘

CH3CH=C

,OTHP

83%

M ‘e

2 ) Me1

Synthesis (1974) 888

Ph3PCH20THP PhLi, THF

’

A Tetrahedron (1975)

85%

2 89

0

I1

0

PhOH +

II Ph-C-CiCH

75%

-----+

PhO I n d i a n J Chem (1975)

13 852

446

COMPENDIUM

VJ

1 ) KNH,

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 367

-cHoCH2CHCH2

90%

’

2 ) CH2iHCH2Br

T e t r L e t t ( 1 9 7 4 ) 1653

1) L-Pr2NLi

MeSC-CCH20Me

93%

MeSC=C=CHOMe

t

I

2) EtBr

Et T e t r L e t t ( 1 9 7 5 ) 1741

BrCH=CHOEt

+

(mMgBr CNi (dpp)C121

i

0’

77%

( 0O m C H =

CHoE

Chem L e t t (1976) 1237

[i-PrCuBrlMgC1 -

+ HzC=C=CHOCH3

i - P r - C u ------+

2 ) H30t

no yield

T e t r L e t t ( i 9 7 6 ) 947

i-PrCOC( -

Me) 2C0zTMS

250”

80%

i-PrC=CMe2

- 1

OTMS JACS ( 1 9 7 5 )

2 1619

SECTION 367

ETHER

-

44 7

OLEFIN OEt

74%

JCS Chem Comm (1975) 519

CH2=CHCH( OEt)2

n-BuMgX,

CuBr

Et20

+

n-BuCH2CH=CHOEt

83%

T e t r L e t t (1975) 3833

95%

S y n t h e s i s (1974) 38

CH2=CH-CHz0SiEt3

1) E - B u L i 2 ) Me1

+

Me-CHzCH=CHOSiEt3 JACS ( 1 9 7 4 )

95%

2 5561

0 68% OMe

OMe JACS ( 1 9 7 4 )

96 7807

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

448

“yo Et30+

SECTION 367

-BF4

i-PrqNEt

’

’

JCS Chem Comm ( 1 9 7 5 ) 6 4 4

95% Can J Chem ( 1 9 7 5 )

Ph

NaOEt

__1

COOEt

Ph

‘::&

53

2005

Ph

70%

OH I n d i a n J Chem ( 1 9 7 6 )

148 4 7 1.50%

Gazz C h i m I t a l ( 1 9 7 5 )

105 2 3 3

93%

T e t r L e t t (1975) 4353

SECTION 367

ETHER

-

OLEFIN

449

71 %

Chem L e t t (1976) 941

CXH

n

1 ) DIBAL-H 2 ) EtOCH2C1

H’

\CH20Et

72%

3 ) H30f Synthesis (1976) 816

78%

PhSex +

JOC (1974)

39 429

1 ) MeSeMe2C- L i t

2 ) Me1

3) t-BUOK,

55% DMSO T e t r L e t t (1976) 457

HOAc \

T e t r L e t t (1974) 4179

450

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 368

JCS Chem Comm (1976) 78

81%

Chem L e t t (1975) 747

1 ) Me1 CH CH OCHPh2

l 2

NMe2

2) anion-exchange r e s i n

H2C=CHOCHPh2

%80%

3) A

Org Synth (1976)

55 3

90% L i e b i g ' s Ann Chem (1974) 523

Section 368

Halide

-

Halide

F'

Ph, t

CH-CHF2

CH: JCS Chem Corn (1975) 715

90%

SECTION 368

HALIDE

PhCH2CH2NH2

t-BuOND

-

HALIDE

451

PhCH2CHBr2

-----+

CuBr2

70% JCS Chem Comm (1976) 433

PhCH2NH2

1 ) CuBrp

RCHBr2

2 ) ( CuBrp-NO)2, CH3CN

JACS (1976)

98

1627

89% T e t r L e t t (1976) 943

PhN2C1 +

CH2=CC12

CUCl

acetone

Org React (1976)

RCH2CHCH3 + SbC15

I Br

cc1

79%

PhCH2CC13

24 225

RCH-CH-CH3

I I

C1 B r T e t r L e t t (1974) 759

70-90%

COMPENOIUM OF ORGANIC SYNTHETIC METHODS VOL 3

452

Q-"'

CH2C12

SECTION 369

0'"' \

88%

c1

JOC (1975)

Section 369

Halide

a-Haloketones. 6-Haloketones.

(Y OSiMe3

-

40

3463

Ketone

......................... ...........................

Page 452-454 454

7 0%

/ NBS, CC14

16% overall Synthesis (1976) 194 and 196

1.60%

Ph

T e t r L e t t (1975) 373

SECTION 369

0

It Me2CH-C-CH3

HALIDE

Br2

CH30H

&J -'& Me

-

453

KETONE

0

II

2.70%

Me2CH-C-CH2Br

Org Synth (1976)

55 24

S02Ph

ether/CH2C1 MgBr2

~

Br&cH3

60%

T e t r L e t t (1976) 3677

62%

T e t r a h e d r o n (1975)

31 231

80%

I I

I

c=o

COCH3

E x p e r i e n t i a (1976)

32

1491

0

11

RICH-CH-C-R

1) Hs(OAC)~

2 ) t-BuOOH

+

RCH( 00-t-Bu )CHBrCOR'

3) Br2 JCS P e r k i n I (1974) 688

50-80%

454

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

0

1I

XI

R-C-CHN2

X = C1, B r

R = alkyl

-70%

R-C-CHIX

+

, aryl

JOC USSR (1976)

Ph-C, Ph-C’

SECTION 370

Ph-C,

CH

CH3C03H

II

Ph-C’

12 228

92%

CHI

II

0

0

JCS P e r k i n I (1975) 1285

RCOOEt

t

-

HCC12Li

H30t ---+

RCOCHC12 moderate t o high y i e l d Comptes Rendus (1974)

278 929

0 t

Br2

--+

Me-SiO

II

PhC-CH2CH2Br quantitative

3

JCS Chem Comm (1974) 1032

Section 370

Phd-) C-CN CH3/

Halide

CC14 ___+

-

Nitrile

Ph\

CHl3’

80%

C-CN

c1 Tetrahedron (1975)

31 1335

SECTION 371

-

HALIDE

NaOH

Ph2CHCN + (CH2Br)2

crown e t h e r

’

OLEFIN

455

CN , Ph C ‘CH2CH2Br

75%

Angew I n t Ed (1974)

S e c t i o n 371

Halide

-

13 665

Olefin

1 ) CuBr, -30” 2 ) MeC-CH

EtMgBr

F

3 ) HgBr2

Et-Br

77%

MeH

4 ) Ere, py S y n t h e s i s (1974) 803

RC-CSiMe3 + HBr

radical -----+

Br R>=CH2

60-95% JOC (1974)

Et-CEC-Et

PhIC12

39

3307

Et-Cl

96%

____+

Cl/--\Et

B u l l SOC Chim France (1975) 2493

PhC-CH

+ PhCH2Br

ZnBr2

PhCH2, f

CH2C12, r f x

c=,c, H

P,h

90%

Br

Gazz Chim I t a l (1975)

105 495

456

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 371

1 ) (cyclohex)2BH 1 ) EtMgBr

n-BuC-CH

+

2 ) MegSiCl

2 ) HOAc, r f x

n-BuC-CSiMe3

3 ) H202

Bu-I

60%

HH -

Bu -SiMe3

H--'

H Bu-H

60%

n1T e t r L e t t ( 1 9 7 4 ) 543

Ph-CzC-Me

CH31F2 CH31

Ph,

C,=C F

M ,e

70%

I' S y n t h e s i s ( 1 9 7 6 ) 473

polymer-PC12

PhCOCH3 ------+

PhCC1=CH2 JACS ( 1 9 7 4 )

96 6469

.I 00%

T e t r L e t t (1976) 895

SECTION 371

HALIDE

-

OLEFIN

457

60%

S y n t h e s i s (1976) 107

C'I F'

c=c

'

"Yi xF

F

Do

1 ) ether/THF,

F

-100"

85%

2 ) H30f

OH

S y n t h e s i s (1976) 761

dBr Br

30%

Rec Trav Chim (1976)

13y::

95 248

AgOTs

A

9 3%

JOC (1976)

fl 384

Me2C-OH

Mg12' Et20 rfx

+

I ( CH2)2CH=CMe2 JCS Chem Comm (1975) 303

100%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

458

PhCOCH2COOEt

+ PC15

PhH

SECTION 372

PhCCl=CHCOOH

50%

JCS Chem Comm (1974) 288

bo (CF3S02)20

Me2CHCOCH3

91 % c1

JOC (1976)

fl 636

Me2C=CMe + Me2CHC=CH2

I OS02CF3

pyridine

Org Synth (1974)

Also v i a :

45% total

I OS02CF3 54 79

A c e t y l e n i c h a l i d e s ( S e c t i o n 308)

S e c t i o n 372

Ketone

. . .

1,2-0i ketones. 1,3-Di ketones. 1,4-Diketones. . 1,5-Diketones. Other diketones.

0

. . . .

-

Ketone

. . . . . . . . . . . . . . . . . . . . . . . Page ......................... ......................... .........................

..........................

Seo2

458-461 461 -463 463-466 466-467 467

90%

EtOH, 6 h r

rfx Org React (1976)

24

261

SECTION 372

KETONE

-

459

KETONE

oD3

87%

0

0

JACS (1976)

0 0

OH 0

I II Ph-CH-C-Ph

3 7868

Yb(N03) 3 HC1, r f x

II I1

95%

Ph-C-C-Ph T e t r L e t t (1975) 4513

46% JOC (1974)

39

2314

d- H 8 CuBr2

DMSO

__*

KI

Na2C03

JOC (1975)

40 1990

Org Synth (1974)

54 37

59%

460

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 3 7 2

45% I

CH2-STs2 Org Synth ( 1 9 7 4 )

P h hh s h Q H H

EE t

S

+=2+ Ph 0 , hv p Lh h E E t

a

1

I-

Me

3 39

CH3CN

80%

0

Chem L e t t ( 1 9 7 5 ) 1 0 3 3

R

xi:'

,

NOCl CH2C12, - 1 5 "

R

)i.f1 NOH JOC ( 1 9 7 4 )

CH3CH2COCH3 + L i N 0 2

EtOH HC1

2 2558

0

1I

65%

CH3C-C-CH3

II

NOH

Can J Chem ( 1 9 7 4 )

Me C=C-NMe2 CN

66-84%

1) PhLi 2 ) 10% H2S04

+

52 1 7 6 0

90%

Me2 CHCOCOPh

JACS ( 1 9 7 5 )

97

2276

SECTION 372

KETONE

-

461

KETONE

50%

kS BZ

Synthesis (1976) 256

c1-

88%

JCS Chem Comm (1976) 804

1 ) BupCuLi, _?-BujP Et20/HMPA, 2 ) AcC1

-70'

92%

T e t r L e t t (1975) 1535

60%

Dokl Chem (1974)

216

404

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

462

Ph3COK

MeCOCH2CH2COOEt

60%

xylene, r f x Z Chem (1975)

15 190

a::"" + R2COCH2COR3

R'

SECTION 372

---CuBr NaH

a

C

O

~O H CH O R ~

R'

(Improved H u r t l e y r e a c t i o n )

Tetrahedron (1975) 31 2607 JCS P e r k i n I ( 1 9 7 5 ) 7 2 6 7

Meoacoo Me0

+ MeCOCH2COMe

CuBr NaH

q

Br

l

l

M

e

98%

COMe

13 340

Angew f n t Chem (1974)

PhCH2Br

+ N i (acac)2

DMF

69%

MeCOCH(CH2Ph)COMe T e t r L e t t (1975) 1727

h

0-1-B~

1 ) NaH

2) EtOAc

78% 0-L-Bu Rec Trav Chim (1976)

95 81

SECTION 372

KETONE

-

-

0

II Pr-C-S-CHCOCH3 I

KETONE

LiBr

+ PhP(CH2CH2CH2NMe2)2

46 3

0

i1

%80%

Pr-C-CHCOCH3

i

MeCN

CH3

CH3 Org Synth (1976)

(!i91 ) (MejSi)2,

BuLi

2 ) Me1

0-I-Bu

55

127

+

91 %

0-~-Bu

3 ) H30t

CH3

Rec T r a v Chim (1976)

Review:

95 81

"The S y n t h e s i s o f 1,4-Di ketones"

A u s t J Chem (1976)

cH3)==NPh

1 ) Et2NLi 2 ) C8H,7Cl

'b NPh

-t

2 339

+

C9H19

CH3

I

CH2CH2

)==-

0

H2S04

0

0

II II CgH1 9CCH2CH2CCH3

C9Hl9 L i e b i g s Ann Chem (1975) 719

464

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

VOL 3

SECTION 372

42%

0

Synth Comm (1976)

6 417

62%

4 ) Cr03, p y r i d i n e JOC (1975)

PhCHO + H2C=CHCOCH3

NaCN DMF A

40 1131

PhCOCH2CH2COCH3

82%

Chem Ber (1974)

0

I1 Et-CH

0

0

+

I1 CH2=CHCMe

Et3N

*

thiazolium s a l t

107 2453

0

II II EtCCH2CH2C-Me T e t r L e t t (1974) 4505

JACS (1974)

96 606

66%

KETONE

SECTION 372

-

465

KETONE

CHO

l,J Chem B e r ( 1 9 7 4 ) O

MeS02CHCOPh t

BrCH2COPh

-Zn/HOAc

2453

PhCOCH2CH2COPh

C o l l Czech Chem Comm (1974)

76%

2 192

82% OH Can J Chem (1976)

b+ PhCOCH2COMe

5

3113

22% AcOH

1 ) NaH, THF, 0" 2 ) E-BuLi 3) CuCl c a t , I2

JOC (1974)

39

3457

75%

( PhCOCH2COCH2b

JOC ( 1 9 7 5 )

40

3887

466

t-BuCOCHj -

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 3

1 ) LDA, T H F 2 ) CuC12, DMF

t-BuCOCH2CH2CO-t-Bu

95%

-

97

JACS ( 1 9 7 5 )

Ag20

73%

2 649

JACS (1975)

Et Me'

, C=NR

1 ) LDA, T H F 2 ) 12, T H F

2912

PhCOCH2CH2COPh

------+ DMSO, A

'

SECTION 372

80%

EtCOCH2CH2COEt

3 ) H30t S y n t h e s i s (1975) 2 5 6

90% RO

CN

JACS ( 1 9 7 4 )

96 5272

66%

Chem L e t t ( 1 9 7 5 ) 89

SECTION 373

KETONE

-

NITRILE

46 7

Fp = n-C5H5Fe(C0)2

JOC (1975)

40 3621

0

II

C1C(CH2)8COC1

t-BuMgC1 C"+

t-BuCO ( CH2 )*COLBU

84%

-78' Aust J Chem (1974)

Review :

27

2525

"Acyl a t i o n o f Enami nes" Chem and I n d (1974) 731

Section 373

PhCH2CN

Ketone

-

1 ) Me2A1C1

2) H20

Nitrile

PhCH2COCH-Ph

I

CN L i e b i g s Ann Chem (1975) 636

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

468

SECTION 374

70%

I

H'

Me

Xe

T e t r L e t t (1976) 683

PhCHO

f

H2C=CCN

CN-

PhCOCH2CH2CN Chem Ber (1974)

&

80%

107 210 0

OTMS

1 ) hv, PhH + CHyCHCN

2 ) aq HCl/MeOH

86%

Chem L e t t (1975) 237

S e c t i o n 374

Ketone

a , B - O l e f i n i c ketones. B , y - O l e f i n i c ketones. y , a - O l e f i n i c ketones.

-

Olefin

. . . . . . . . . . . . . . . . . . . . . .page ....................... .......................

469-485 485 486-488

For t h e o x i d a t i o n o f a l l y l i c a l c o h o l s t o o l e f i n i c ketones, see S e c t i o n 168. V o l . 1 (Ketones from A l c o h o l s and Phenols). For t h e o x i d a t i o n o f a l l y l i c methylene groups (C=C-CH .+ C=C-CO), see S e c t i o n 170, Vol. 1 and 2 (Ketones from A l k y l s and Gethylenes). For t h e a l k y l a t i o n o f o l e f i n i c ketones, see a l s o S e c t i o n 177, V o l . 1 and 2 (Ketones from Ketones) and S e c t i o n 74 ( A l k y l s from O l e f i n s ) , Vol. 3, f o r c o n j u g a t e a1 k y l a t i o n s .

SECTION 374 0

II

PhpC-C-Br

I

KETONE Zn, THF

------+

-

OLEFIN

469

95%

Ph2C=C=0

Br

JCS Perkin I (1975) 1600

Ac20 + B u 3 A l * N B u 3

130"

xyl ene

CH2=C=0

80%

J Organometal Chem (1975) 97 21

55%

JOC (1976) 5 2939

1 ) L-BuOkLCH2PPh3

2) RCOR' 3) R"L1

'

RmR'' 50-80%

R'

0

JOC (1974) 39 629

470

COYPENDIUM

Me2C=CHCOMe

OF ORGANIC SYNTHETIC METHODS VOL 3

+ PhP=C=C(OLi)Ph

HMPA

0 35% Ph

T e t r a h e d r o n (1975)

Me

I

1 ) BuLi

( Et0)2P-N-CH=C=CH2

II0

____+

2 ) BzBr

SECTION 374

31 1331

65%

PhCH2C-CH=CH2

II

0

T e t r L e t t ( 1 9 7 6 ) 835

1) i-Eu2AlH

-t-Bu-C-CH

2 ) BuLi 3,

68%

d

CH2CMe

il

0

0 JCS Chem Comrn ( 1 9 7 6 ) 17

1 ) PC15

I

COCH3

2 ) PhCHO

80%

I

c=o

I

CH=CHPh E x p e r i e n t i a (1976)

32

1491

92% Gazz Chim I t a l (1975)

105 109

SECTION 374

KETONE

Me2NCH=CH-CH( OEt)2 + PhCOCH3

-

-

OLEFIN

471

Me2NCH=CHCH=CHCOPh

74%

L i e b i g s Ann Chem (1975) 874

1 ) LDA, PhSSPh

%70%

2 ) oxidation, A

0 4

1 ) NaH, BuLi

’

JACS (1976)

98 4887

JACS (1976)

98 4087

‘x ’0

JCS Cheni Comm (1974) 497

1 ) LDA 2 ) BzBr

Bz

55%

JCS Chem Comm (1975) 72

472

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 374

66%

JACS (1975)

97

5434

70% 3OC (1975) 4 2 2976

& b, Ph3P

_ I +

CC14

c1 S y n t h e s i s (1975) 708

tL

Ph3PC12

91 %

E t 3 N , benzene Synth Comm (1975)

2

19.3

KETONE

SECTION 374

-

OLEFIN

473

1 ) (Et0)3A1 OR

2 ) (i--Pr)2NLi,

%50%

A

JACS (1974)

96 61 53

54%

S y n t h e s i s (1974) 33

phv

86%

Et

Angew I n t Ed (1975)

e

CH20H

14 499

qo

90%

B u l l SOC C h i m Fr (1974) 1015

474

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 374

49% JCS P e r k i n I (1974) 964

PdC12, HC1 HOAc/dioxane

i-Bu

64%

’

4

M

e

i-Bu

-

Synthesis (1976) 240

>F

WCBH”” t-butylchromate

‘8”17

0

I n d i a n J Chem (1975)

40%

13 29

7 0%

Synth Comm (1976)

5 217

KETONE

SECTION 374

-

OLEFIN

475

O\PPh2

I

'OPh2

1 ) base, TsCl

1) BuLi

2 ) CF3COOH

2 ) MeCHO

3 ) BuLi, O2

JCS Chem Comm (1975) 148

TiC14

83%

S y n t h e s i s (1 974) 667

1 ) PhMgBr

Ph 83%

2 ) NCS, LiO-t-Bu Ph' Chem L e t t (1976) 771

. hu

JOC (1975)

1865

hu, E t O H

30%

02, r o s e bengal OH Comptes Rendus C (1974)

279

347

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

476

1 ) 3 0 % H202, HOAc, Hf

SECTION 374

CH2COOMe

42%

2 ) K2C03, M e 1

OMe

S y n t h Comm (1975)

5

161

1 ) SnC14, CH2C12 2 ) L i F , DMF

90%

YY 0

T e t r L e t t (1974) 3197

t-Bu,

H

/C=C’

Me

L-Bu,

CH3COC1

F

‘HgC1

A1C13

c=, H

cM,e

‘C-CH3

99%

II

0

T e t r L e t t ( 1 9 7 6 ) 3097

TMSCHzCHTMS

PhCH=CHSiMe3

PhCOCl

f

f

-

PhCH2COC1

A1C13 -20“

-

TMSCH=CHCOPh

80%

B u l l SOC C h i m F r (1975) 2143 PhCH=CHCOCH2Ph J C S Chem Comm (1975) 633

86%

SECTION 374

KETONE

-

OLEFIN

477

97% 97% o p t i c a l p u r i t y

(prochiral)

JOC (1974)

%.g

39 1615

1 ) MVK

3) aldol

0

JOC (1976)

5 3337

78%

JOC (1976)

93767

478

COMPENDIUM

EtCOCH2CH2C1 e T s O H , PhH

OF ORGANIC SYNTHETIC METHODS VOL 3

+@

SECTION 374

0

T e t r L e t t (1975) 5 2 7

0 COCH3

------+

2 ) -OH

z

-

“‘OH

0

Chem L e t t (1976) 1025

1 ) PhCH=CHCOPh Sph

2 ) Cu’,

H20/MeCN

’ 59%

Ph JOC (1976)

41 2506

-A

SECTION 374

KETONE

- OLEFIN

479

1 ) piperidine, -H20

45%

23 ) MVK HOAc, NaOAc, H20

Synth Comm (1976)

.,;!Sd /

-

L-phenylalanine HC104

estrone

~

6 237

& N

82% y i e l d 82% ee

JACS (1975)

97

5282

Pure and Appl Chem (1975)

48 317

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

480 CH3CH2COOH

1) CH2=CHLi 2 ) H20

CH3CH2COCH=CH2

SECTION 374 92%

Tetr Lett (1974) 2877

Can J Chem (1974) 52 2157

0

1 ) i-PrpNLi 2 ) phexyl I

](=HC2HCrP-n

+

3) hydrolysis

COOMe

7 ) PhSCH21 2 ) NaI04 3j n

+

It

n-PrCH=CH-C-hexyl

81 %

Tetr Lett (1975) 925

CH2=CH-COCH2COOMe JOC (1974)

72%

2 2648

1 ) PhMgBr or PhCu

77%

2 ) H30t

JOC (1976) 41 - 2935; 2937

SECTION 374

KETONE

-

OLEFIN

80%

JOC (1975)

(3

">-/ Et2N-i Li

+

PhCOOCH3

+

0

40 2570

H Et

95%

M -C

I1

0

Angew I n t Ed (1976)

15 171

Me2C u L i

OMe

70% Me

I n d i a n J Chem (1974) 12 325 Chem Comm (1974) 1005-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

482

SECTION 3 7 4

EtMgBr

61 %

___r

B u l l SOC C h i m F r a n c e ( 1 9 7 6 ) 439

TMSO 72%

OMe

CHO JACS ( 1 9 7 4 )

96 7 8 0 7

S y n t h Comm ( 1 9 7 5 )

Ph

5 27

1 ) LDA, THF

61 %

2 ) T i C 1 3 , HCI, H20 Angew I n t Ed ( 1 9 7 6 )

15 50

KETONE

SECTION 374

OLEFIN

483

1 ) :CC12 2) MeLi, -95"

EtO

R

-

Rl

40-50%

3) H ~ O + Me T e t r L e t t (1974) 3297

y 2

MeCOCH2Me

1 ) Me2NCH=CMe +

MeCOC=CHCOMe

I

Na H 2) S i gel

Me high y i e l d s Chem Ber (1974)

PhCH2COPh +

PhN=CHOEt

190"

107 1499

PhCCOPh

61%

II

CHNHPh 2 Chem (1975)

g%'
+ cH(COOEt)2

DMSO

THF

15

(EtO2C),CHCH2CH=CHC0Et

100%

COEt T e t r L e t t (1975) 2591

1 ) L i -HMPA-THF-EtOH Me0

60%

2 ) HC1 JOC (1975)

40 2841

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

484

SECTION 374

1) TiC14 2 ) $0

3 ) benzene, TsOH, -H20 83%

+y 97% ee Chem L e t t (1976) 279

a

1 ) (COOEt)2

90%

2 ) PhCHO

T e t r Lett (1976) 4691

90%

JACS (1976)

MeCOC-C02

I

(CH3I2

electrolysis

98 4577

90%

MeCOC=CH2

I

CH3 Comptes Rendus C (1975)

280 731

SECTION 374

KETONE

-

OLEFIN

Comptes Rendus

485

C (1976) 282 761

J Organometal Chem (1976)

OH

TsOH --*

benzene Ph

&

Ph

Ph

Fe(C0)3

+

A1C13

110 121

90%

Ph

H e l v Chim A c t a (1976)

PhH

__+

moderate y i e l d T e t r L e t t (1974) 3789

59 2012

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOC 3

486

SECTION 374

30%

JCS Perkin I (1974) 2240

TMSCH2CH=CH2 + PhCOCl

A1 C1

PhCOCH2CH=CH2

90%

J Organometal Chem (1975)

Me2C- CO- CHMe +

I

Br

I

Br

0

85 149

Zn

78%

M

e

p e Mv '

Tetr Lett (1975) 4487

70%

PhH, 0' Helv Chim Acta (1974)

Me2CuLi

+ CH2=CH &OMe

Et20 -200

57

MeCH2CH=CHCH2CH2COMe

Synthesis (1975) 317

164

81%

SECTION 374

KETONE

-

OLEFIN

487

90%

T e t r L e t t (1974) 3365

+ [CH2=C(OEt)12CuLi

-THF -+

-78'

&

84%

C=CH2

I

OEt

JCS Chem Comm (1975) 519 JACS (1975)

97

3822

96%

T e t r L e t t (1975) 3901

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

488

Q

SECTION 374

1 ) LDA

H;qH

OMe

2 ) a1 l y l bromide 3 ) H30t 80%

>90% ee JACS (1976)

98 3032

B u l l Chem SOC Jap (1974)

X H

0

It

EtOCO

EtOCO

1 ) RCOCl COR

2 ) A1C13, CS2

Comptes Rendus (1974)

Also v i a :

2526

A c e t y l e n i c ketones ( S e c t i o n 309) 6-Hydroxyketones ( S e c t i o n 330)

278

267

SECTION 376

S e c t i o n 375

NITRILE

Nitrile

-

-

OLEFIN

489

Nitrile

90%

Chem L e t t (1976) 147

S e c t i o n 376

RCH2CH2CN

Nitrile

-

Olefin

1 ) LDA, -75"

JN

+

J

90%

R

T e t r L e t t (1974) 2279

96% Angew I n t Ed (1975)

TMS

I

MeC-CN

I

+ EtCOMe

-

Li

3 179

Me,

M ,e h = C Et'" 'CN

95% T e t r L e t t (1974) 4005

PhCHO

+ CH3CN

KOH crown e t h e r

+

PhCH=CHCN

T e t r L e t t (1976) 3495

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

490

cuo2

CH~(CO~H)CN

PhCHO

NaOH

SECTION 376

Ph

~40% Ph

CN

B5N02 - "$ T e t r L e t t ( 1 9 7 5 ) 3843

>-I-

CN

t

Na'

HYT

63%

COOEt Chem L e t t ( 1 9 7 6 ) 757

2

CH 'COOEt

SOCl THF, r f x

COOEt

CN 64%

NC

COOEt S y n t h Comm ( 1 9 7 6 )

PhCXH

1) CNi21CN)2(DPB)31 2 ) HC1

+

6

185

PhCH=CHCN

70%

Gazz Chim I t a l ( 1 9 7 4 )

PhCHCN

I

Et

H C X H , KOH, DMSO phase-transfer c a t

104 1 2 7 9

CH=CH2

I

Ph-C-CN

60%

I

Et Org Synth (1976)

55 9 9

SECTION 377

OLEFIN

S e c t i o n 377

Olefin

-

-

OLEFIN

491

Olefin

..................... .page ............................ ............................ ............................

,Z-Oienes ( A l l e n e s ) . ,3-Dienes. ,4-Dienes. ,5-Di enes.

qui no1 ine Me2C=CCH3

+

100"

I

70%

Me C=C=CH2 2

OTf JOC (1975)

R3MgX, CuBr

R'CsCCH-OTs

THF

t

40 647

1 ) RI2CuLi

3

2 ) MeI, 0"

90%

R3R'C=C=CHR2

Rec Trav Chim (1975)

RCzCSMe

R \c=c=c=c

/

99 112

R

20-50%

R' e

R'/

491-493 493-495 495 495

T e t r L e t t (1975) 2923

P,h Ph2C=C=C\

CUCl

Br

DMF

Ph2C=C=C,

P,h /

C=C=CPh2

P6

JCS Chem Comm (1975) 174

72%

492

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 377

33% ee

JACS (1975) 2 2919

430%

Tetr Lett (1974) 1275

oNe c/"" & MeLi CBr4

Na/NH3

w

___f

95%

65%

Synthesis (1975) 194

Me2CuLi

,H

Me

,c=c=c

3

JCS Chem Comm (1976) 183

80%

SECTION 377

6 -

OLEFIN - OLEFIN

493

H\C/Pr

AcOoCXH

PrMgI

II

72%

Angew I n t Ed (1976)

496

DMF a c e t a l

94%

70" OH H e l v Chim Acta (1975)

58

1450

SMe Me2C=CHCH2SCHMeS(0)Me

1 ) LDA, -10'

+

I

54%

CH2=CHCMe2C=CH2

2 ) Me1 Comptes Rendus (1975)

280

1231;1327

58%

JACS (1975)

2 3252

494

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 3

SECTION 3 7 7

OH

I

I-

[(PhO),PCH31t

7 8J

HMPT, 50" S y n t h e s i s ( 1 9 7 6 ) 108

+ R 3 CH=CHR 4

R ' R 2 C=CHBr

Et3N L2Pd(OAc)2,

100"

R'R2C=CHCR3=CHR4

JOC ( 1 9 7 5 )

CH2=CHCH=CH2

(Ph3P)2NiBr2 NaBH4, THF-EtOH,

100"

+

CH2=CHCH=CHCH2CH=CHMe

JACS ( 1 9 7 5 )

EtCXEt

1) H2BC1

40 1083

97

95%

341

Et

100%

2) MeCu

Et

Et

JACS ( 1 9 7 5 )

97

5606

Ph 80% Ph

CH2C1 2, hv

Ph Ph S y n t h Comm ( 1 9 7 6 )

6 309

SECTION 377

OLEFIN

-

OLEFIN

495 Me

t

Ph3PCH2CH=CHCH2PPh3

0

C=CH2

85%

t-BUOK, E t 2 0 , L-BuOH

I

CH3 JOC ( 1 9 7 5 )

PhCfCR

t

((Ni))

40 100

- ----

Ph

HC1

50%

J O r g a n o m e t a l Chem ( 1 9 7 5 ) .9 6 C19

1 ) LDA. THF, -78" PhSe(0)CH3

PhCH=CHCH2CH=CHPh

+

2 ) PhCH=CHCH2Br

75%

3 ) HOAc

4 ) CH2C12, r f x JACS ( 1 9 7 5 )

CH2=CHCH=CH2

1 ) t - B u C u , MgBr2 +

t-

97

3250

BuCH2CH=CHCHF

90%

2 ) -Br

J O r g a n o m e t a l Chem ( 1 9 7 5 ) .9_2 C28

1 ) 5-BuLi ~-PrSCH2CH=CH2

, -25"

2 ) CUI, -78"

--+

i-PrSCH=CHCH2CH2CH=Cti2

3 ) CH2=CHCH2Br B u l l Chem SOC Japan ( 1 9 7 5 ) 4 2 1 5 6 7

88%