Radical Reactions in Organic Synthesis

by Zard, Samir Z.

• ISBN13: 9780198502401
• ISBN10: 0198502400
• Format: Paperback
• Copyright: 2004-01-01
• Publisher: Oxford University Press

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.

Author Biography

Professor Samir Z. Zard is currently Professor of Organic Chemistry at Ecole Polytechnique, France and Director of Research at the Centre National de la Recherche Scientifique, France

Table of Contents

Preface	v
Introduction and some general concepts	1	(15)
A brief history	1	(5)
Timescales: the importance of reaction rates	6	(2)
Further comparison with ionic reactions	8	(1)
A few words on the structure, stability, and reactivity of radicals	9	(3)
Chain reactions	12	(4)
General principles: chain reactions based on stannane chemistry	16	(42)
A simple chain reaction based on organotin hydrides	16	(3)
Some examples	19	(2)
The Barton--McCombie and related deoxygenation of alcohols	21	(3)
Reduction of C--N bonds	24	(2)
Additions to olefins: general considerations	26	(1)
Intermolecular additions to olefins: polar and steric effects	27	(3)
Intermolecular additions to olefins: some synthetic applications	30	(2)
Intramolecular additions to olefins---rates and regiochemistry	32	(2)
Intramolecular additions to olefins: synthetic applications	34	(7)
Some stereochemical aspects of radical cyclizations	41	(2)
Some further synthetic variations	43	(4)
Nitrogen- and oxygen-centered radicals	47	(11)
Further chain reactions of stannanes	58	(37)
Radical rearrangements	58	(1)
Opening and closure of 3- and 4-membered rings	58	(3)
Opening of small rings: some synthetic applications	61	(3)
Formation of small rings	64	(2)
1,2-shift of unsaturated groupings and related rearrangements	66	(5)
Ring opening of 5-membered and larger rings	71	(4)
Radical translocation by intramolecular hydrogen transfer	75	(5)
Stannyl radical generation by fragmentation	80	(4)
Variations on the fragmentation theme	84	(1)
Some aspects of the stereochemistry of radical reactions	85	(2)
Some concluding remarks	87	(8)
Organo-silicon, -germanium, and -mercury hydrides	95	(15)
Silicon and germanium derivatives: general, considerations	95	(1)
Radical reactions with germanium	95	(1)
Radical reactions with silicon: tris(trimethylsilyl)silane	96	(4)
Other silanes	100	(1)
Polarity reversal catalysis	101	(1)
Chain reactions of organomercury hydrides	102	(1)
Organomercury hydrides: synthetic applications	103	(7)
The Barton decarboxylation and related reactions	110	(25)
Some early radical decarboxylation processes	110	(1)
The Barton decarboxylation: early experiments	111	(1)
The radical chemistry of Barton thiohydroxamate esters	112	(3)
Functional group transformations via Barton esters	115	(6)
Carbon--carbon bond formation	121	(5)
Generation of carbon radicals from alcohols	126	(1)
Generation of nitrogen- and oxygen-centered radicals	127	(2)
Some related processes	129	(6)
Atom and group transfer reactions	135	(41)
Kharasch-type processes: an overview	135	(1)
Degeneracy and the lifetime of the intermediate radicals	136	(1)
Transfer of hydrogen atoms	137	(8)
Halogen atom transfer	145	(7)
Transfer of sulfides, selenides, tellurides, and nitriles	152	(1)
Transfer of xanthates and related dithiocarbonyl derivatives	153	(10)
Further applications of degenerate processes: some chain reactions of sulfones	163	(4)
Radicals from organoboron compounds	167	(9)
The persistent radical effect: non-chain processes	176	(17)
Selective suppression of fast modes: the Fischer-Ingold effect	176	(1)
Dissociation of nitroso derivatives	177	(2)
Photolysis of nitrite esters: the Barton reaction	179	(2)
Amidyl radicals by photolysis of nitrosamides	181	(1)
Photolysis of hypoiodites, N-iodoamides, and sulfenates	181	(3)
Mimicking vitamin B12: the radical chemistry of organocobalt derivatives	184	(5)
Living free-radical polymerizations	189	(4)
Redox processes	193	(52)
Electron transfer processes	193	(1)
Formation of radicals by oxidation with transition metal salts: general reaction scheme	194	(2)
Oxidations involving Mn(III) and Cu(II)	196	(7)
Oxidations involving Fe(III), Ce(IV), Ag(II), and Pb(IV)	203	(2)
Formation of radicals by reduction with transition metal salts: general reaction scheme	205	(2)
Reductions with Cr(II) and Ti(III) salts	207	(4)
Reduction with Sm(II) iodide	211	(8)
Reductions with iron, copper, and ruthenium salts or complexes	219	(5)
Dissolving metal reductions	224	(4)
Electron transfer from organic reducing agents	228	(2)
Electrochemical and photochemical redox processes	230	(4)
A word on SRN1 reactions	234	(11)
Some concluding remarks	245	(6)
A brief overview and some practical considerations	245	(2)
Nature's radical chemistry	247	(4)
Index	251