Motherwell / Crich / Meth-Cohn Free Radical Chain Reactions in Organic Synthesis

1. Auflage 2013
ISBN: 978-0-08-092495-3
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 288 Seiten, Web PDF

Reihe: Best Synthetic Methods

Written for both the experienced practitioner and the newcomer, this book provides essential guidance to the practical aspects of free radical chain reactions. The book presents tried and tested synthetic schemes as well as a selection of recently developed methods describing rationally designed, highly efficient syntheses giving high yield interconversions of functional groups and carbon*b1carbon bond formation under mild, neutral conditions. Written by two experienced practitioners in the field, this volume explodes the myth that free radicals are highly reactive, non-selective intermediates. - Contains an extensive introduction discussing principles, advantages, and disadvantages of radical chain reactions - Demonstrates functional group interconversions by radical chain reactions - Lists carbon*b1carbon bond formations - Presents inter- and intramolecular radical chain reactions - Includes many examples and experimental details selected by experienced practitioners in this field

Autoren/Hrsg.

Motherwell, William B.

Crich, David

Meth-Cohn, O.

Inhaltsverzeichnis

1;Front Cover
;1
2;Free Radical Chain Reactions in Organic Synthesis;4
3;Copyright Page
;5
4;Table of Contents
;6
5;Dedication
;7
6;Foreword;8
7;Preface;10
8;Detailed Contents;12
9;Chapter 1. Some basic concepts of free radical chain reactions;22
9.1;1.1 Introduction;22
9.2;1.2 The advantages;22
9.3;1.3 The relative "character" of various radical species;23
9.4;1.4 Determinant factors in the production of a successful free radical chain reaction;28
9.5;1.5 The initiation ceremony;31
9.6;1.6 Strategy and design in synthetic sequences involving carbon centred radical reactions;33
9.7;1.7 Some practical guidelines;40
9.8;1.8 Overview and perspectives;45
9.9;References;46
10;Chapter 2. Books and review articles;48
10.1;2.1 Some earlier basic texts and reviews (pre-1980);48
10.2;2.2 General books and reviews (post-1980);49
10.3;2.3 Recent books and articles dealing with more specific aspects of free radical reactions;49
11;Chapter 3. Substitution reactions;50
11.1;3.1 Dehalogenation (RX . RH, X = halogen);50
11.2;3.2 Deoxygenation reactions (ROH . RH);58
11.3;3.3 Deamination reactions (RNH2 . RH);79
11.4;3.4 Denitration reactions (RNO2 . RH);86
11.5;3.5 Reductive homolytic cleavage of the carbon–sulphur bond;92
11.6;3.6 Deselenation reactions;100
11.7;3.7 Decarboxylation reactions;106
11.8;3.8 Functional group interchange using organometallic derivatives of boron, mercury and cobalt;134
11.9;References;145
12;Chapter 4. Olefin forming ß-elimination reactions;152
12.1;4.1 Introduction;152
12.2;4.2 Alkenes from vicinal dihalides;152
12.3;4.3 Alkenes from vicinal diols via 1,2-bis-xanthate esters;154
12.4;4.4 Alkene formation by stannane induced fragmentation of thiocarbonyl-O-ester derivatives of ß-hydroxy sulphides, sulphones and isocyanides;156
12.5;4.5 Olefin formation from ß-halogeno sulphides, sulphoxides, sulphones and selenides;160
12.6;4.6 Alkenes from vicinally functionalized nitro derivatives;162
12.7;References;165
13;Chapter 5. Preparative free radical rearrangement reactions;168
13.1;5.1 Introduction;168
13.2;5.2 Acetoxyl group migration reactions;169
13.3;5.3 Radical rearrangements involving allylic systems;172
13.4;5.4 The cyclopropylcarbinyl–homoallylic radical rearrangement;176
13.5;5.5 Homobenzylic rearrangements;184
13.6;5.6 Determinental factors in some miscellaneous radical induced carbocyclic ring cleavage reactions;186
13.7;5.7 Ring opening reactions of epoxides by a neighbouring carbon centred radical;187
13.8;References;197
14;Chapter 6. Intermolecular carbon–carbon bond forming free radical chain reactions;200
14.1;6.1 Addition of carbon centred radicals to multiple bonds;200
14.2;6.2 Stereochemical aspects;202
14.3;6.3 Addition to alkenes with chain transfer by hydrogen atom abstraction;204
14.4;6.4 Addition to alkenes with chain transfer by formation of a carbon–heteroatom bond;216
14.5;6.5 Addition to alkenes with concomitant displacement of a chain carrying radical;223
14.6;6.6 Addition to alkynes;228
14.7;6.7 Carbon–carbon bond formation by homolytic substitution at an sp3 carbon;229
14.8;References;230
15;Chapter 7. Intramolecular carbon–carbon bond forming free radical chain reactions;234
15.1;7.1 Preparation of five membered rings by 5-exo cyclizations;234
15.2;7.2 Preparation of six membered rings by 6-exo cyclizations;259
15.3;7.3 Preparation of seven membered and medium sized rings;263
15.4;7.4 Preparation of large rings;266
15.5;7.5 Transannular cyclizations;268
15.6;7.6 Hydrogen atom abstraction/cyclizations;269
15.7;7.7 Formation of endo mode products by cyclization of stabilized radicals;270
15.8;7.8 Tandem processes;271
15.9;7.9 Radical cyclizations by SH2 at carbon;274
15.10;References;275
16;Index;280