Radical reactions in organic synthesis / Samir Z. Zard.

Format:

Book

Author/Creator:

Zard, Samir Z.

Series:

Oxford chemistry masters ; 7.

Oxford chemistry masters ; 7

Language:

English

Subjects (All):

Free radical reactions.

Organic compounds--Synthesis.

Organic compounds.

Physical Description:

xi, 256 pages : illustrations ; 25 cm.

Place of Publication:

Oxford ; New York : Oxford University Press, 2003.

Summary:

Samir Zard provides a description of radical reactions and their applications in organic synthesis. This book shows that an with an elementary knowledge of kinetic and some common sense, it is possible to harness radicals into a tremendously powerful tool for solving synthetic problems.

Contents:

1.1 A brief history 1

1.2 Timescales: the importance of reaction rates 6

1.3 Further comparison with ionic reactions 8

1.4 A few words on the structure, stability, and reactivity of radicals 9

1.5 Chain reactions 12

2 General principles: chain reactions based on stannane chemistry 16

2.1 A simple chain reaction based on organotin hydrides 16

2.2 Some examples 19

2.3 The Barton-McCombie and related deoxygenation of alcohols 21

2.4 Reduction of C-N bonds 24

2.5 Additions to olefins: general considerations 26

2.6 Intermolecular additions to olefins: polar and steric effects 27

2.7 Intermolecular additions to olefins: some synthetic applications 30

2.8 Intramolecular additions to olefins

rates and regiochemistry 32

2.9 Intramolecular additions to olefins: synthetic applications 34

2.10 Some stereochemical aspects of radical cyclizations 41

2.11 Some further synthetic variations 43

2.12 Nitrogen- and oxygen-centered radicals 47

3 Further chain reactions of stannanes 58

3.1 Radical rearrangements 58

3.2 Opening and closure of 3- and 4-membered rings 58

3.3 Opening of small rings: some synthetic applications 61

3.4 Formation of small rings 64

3.5 1,2-shift of unsaturated groupings and related rearrangements 66

3.6 Ring opening of 5-membered and larger rings 71

3.7 Radical translocation by intramolecular hydrogen transfer 75

3.8 Stannyl radical generation by fragmentation 80

3.9 Variations on the fragmentation theme 84

3.10 Some aspects of the stereochemistry of radical reactions 85

4 Organo-silicon, -germanium, and -mercury hydrides 95

4.1 Silicon and germanium derivatives: general, considerations 95

4.2 Radical reactions with germanium 95

4.3 Radical reactions with silicon: tris(trimethylsilyl)silane 96

4.4 Other silanes 100

4.5 Polarity reversal catalysis 101

4.5 Chain reactions of organomercury hydrides 102

4.6 Organomercury hydrides: synthetic applications 103

5 The Barton decarboxylation and related reactions 110

5.1 Some early radical decarboxylation processes 110

5.2 The Barton decarboxylation: early experiments 111

5.3 The radical chemistry of Barton thiohydroxamate esters 112

5.4 Functional group transformations via Barton esters 115

5.5 Carbon-carbon bond formation 121

5.6 Generation of carbon radicals from alcohols 126

5.7 Generation of nitrogen- and oxygen-centered radicals 127

5.8 Some related processes 129

6 Atom and group transfer reactions 135

6.1 Kharasch-type processes: an overview 135

6.2 Degeneracy and the lifetime of the intermediate radicals 136

6.3 Transfer of hydrogen atoms 137

6.4 Halogen atom transfer 145

6.5 Transfer of sulfides, selenides, tellurides, and nitriles 152

6.6 Transfer of xanthates and related dithiocarbonyl derivatives 153

6.7 Further applications of degenerate processes: some chain reactions of sulfones 163

6.8 Radicals from organoboron compounds 167

7 The persistent radical effect: non-chain processes 176

7.1 Selective suppression of fast modes: the Fischer-Ingold effect 176

7.2 Dissociation of nitroso derivatives 177

7.3 Photolysis of nitrite esters: the Barton reaction 179

7.4 Amidyl radicals by photolysis of nitrosamides 181

7.5 Photolysis of hypoiodites, N-iodoamides, and sulfenates 181

7.6 Mimicking vitamin B[subscript 12]: the radical chemistry of organocobalt derivatives 184

7.7 Living free-radical polymerizations 189

8 Redox processes 193

8.1 Electron transfer processes 193

8.2 Formation of radicals by oxidation with transition metal salts: general reaction scheme 194

8.3 Oxidations involving Mn(III) and Cu(II) 196

8.4 Oxidations involving Fe(III), Ce(IV), Ag(II), and Pb(IV) 203

8.5 Formation of radicals by reduction with transition metal salts: general reaction scheme 205

8.6 Reductions with Cr(II) and Ti(III) salts 207

8.7 Reduction with Sm(II) iodide 211

8.8 Reductions with iron, copper, and ruthenium salts or complexes 219

8.9 Dissolving metal reductions 224

8.10 Electron transfer from organic reducing agents 228

8.11 Electrochemical and photochemical redox processes 230

8.12 A word on S[subscript RN]1 reactions 234

9.2 Nature's radical chemistry 247.

Notes:

Includes bibliographical references and index.

ISBN:

0198502419

0198502400

OCLC:

52876699