General and synthetic methods., Volume 3

400 Pages·1980·24.85 MB·english

by  G. Pattenden

General and Synthetic Methods
Volume 3

A Specialist Periodical Report
General and Synthetic Methods
Volume 3
A Review of the Literature Pub ished during 1978
Senior Reporter
G. Pattenden, Department of Chemistry, University of Nottingham
Reporters
K. Cooper, University of Nottingham
A. B. Holmes, University of Cambridge
D. C. Howell, Lilly Research Centre, Windlesham, Surrey
M. G. Hutchings, I.C.I. Organics, Manchester
R. C. F. Jones, University of Nottingham
G. Kneen, Wellcome Research Laboratories, Beckenham, Kent
D. W. Knight, University College, Cardiff
M. Mellor, Bush Boake Allen Ltd., London
S. M. Roberts, University of Salford
W. J. Ross, Lilly Research Centre, Windlesham, Surrey
D. J. Thompson, /.C./. Organics, Manchester
S. Turner, Polytechnic of North London
The Chemical Society
Burlington House, London, WIV OBN
British Library Cataloguing in Publication Data
General and synthetic methods.-
(Chemical Society. Specialist periodical reports).
VOl. 3
1. Chemistry, Organic-Synthesis
I. Pattenden, Gerald 11. Series
547l.2 QD262
ISBN 0-85186-730-8
ISSN 0141-2140
Copyright @ 1980
The Chemical Society
All Rights Reserved
No part of this book may be reproduced or transmitted
in any form or by any means -graphic, electronic,
including photocopying, recording, taping or
information storage and retrieval systems - without
written permission from The Chemical Society
Set in Times on Linotron and printed offset by
J. W. Arrowsmith Ltd., Bristol, England
Made in Great Britain
In trod uc ti0 n
This report on General and Synthetic Methods is similar in scope and format to
the previous two volumes in the series. Developments in the synthesis of saturated
heterocycles, unfortunately omitted from Volume 2, are covered in this volume
(Chapter 8), and a special report on ‘Photochemistry in Synthesis’ (Chapter 10) is
included.
There have been several high points in synthesis during 1978, but perhaps one
should use this opportunity to single out the achievements of one chemist, the
illustrious E. J. Corey, who during 1978 reported first total syntheses of gib-
berellic acid, the plant growth regulator (Chapter 7, ref. l),e rythronolide B, the
aglycone of the erythromycin B family of antibiotics (Chapter 9, ref. 17)’ and of
N-methylmaysenine, one of the antitumoural maytensenoids (Chapter 9, ref. 23),
each a major achievement in synthesis design and execution.
July 1979 G. PATTENDEN

Cont ents
Chapter 1 Saturated and Unsaturated Acyclic
Hydrocarbons 1
By D. C. Horwell
1 Introduction 1
2 Saturated Hydrocarbons 2
3 Olefinic Hydrocarbons 4
4 Conjugated 1,3-Dienes 19
5 1,4-, 1,5, and 1,6-Dienes 24
6 Allenic Hydrocarbons 27
7 Acetylenic Hydrocarbons 29
8 Enynes and Polyunsaturated Hydrocarbons 32
Chapter 2 Aldehydes and Ketones 36
By.S . M. Roberts
1 Preparations of Aldehydes and Ketones 36
By Oxidation of Alcohols 36
Thio- and Seleno-ketones 37
Cyclic Ketones 37
Dicarbonyl Compounds 39
Other Preparations 41
2 Reactions of Aldehydes and Ketones 46
Alkylation 46
Aldol Reactions 48
Reduction 49
General Reactions 50
3 Preparations of Unsaturated Aldehydes and Ketones 54
4 Reactions of Unsaturated Aldehydes and Ketones 60
Alkylation 60
vii
...
Vlll General and Synthetic Methods
Reduction 61
Conj ugate Addition 62
General Reactions 65
5 Protected Aldehydes and Ketones 66
Preparation 66
Regeneration of Aldehydes and Ketones 67
Reactions 68
6 Halogeno-derivatives 71
Preparation 71
Reactions 72
7 Acyl, Homoenolate, Acylvinyl, and Dienolate Anion
Equivalents 73
Chapter 3 Carboxylic Acids and Derivatives 75
By D. W. Knight
1 Introduction 75
2 Carboxylic Acids 75
General Synthesis 75
Diacids 77
Hydroxy- acids 77
Keto-acids 78
Unsaturated Acids 80
Decarboxylation 83
Protection and Deprotection 84
3 Lactones 85
/3-Lactones 85
Butyrolactones 86
Butenolides and Tetronic Acids 89
-Methylenebutyrolactones 93
LY
Valerolactones 96
4 Macrolides 98
5 Esters 100
Esterification 100
General Synthesis 101
Diesters 104
Hydroxy- esters 106
Keto-esters 107
Unsaturated Esters 109
Thioesters and Related Compounds 114
6 Carboxylic Acid Amides 117
Synthesis 117
Reactions 120