Reagents for Radical and Radical Ion Chemistry E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Handbook of Reagents for Organic Synthesis
• Sprache: Englisch

Seitenzahl: 2080

Veröffentlichungsjahr: 2013

Beschreibung

Radicals and radical ions are important intermediates with wide use in organic synthesis. The first book to concentrate on reagents for the creation and use of radicals and radical ions, this new volume in the Handbooks of Reagents for Organic Synthesis series compiles articles taken from the e-eros database, on reagents for use in radical and radical chemistry, to help the chemist in the lab choose the right reagents. Reflecting the enormous growth of radical chemistry over the past ten years, this is an essential guide for all synthetic chemists.

Leseprobe

Contents

Cover

Other Titles in this Collection

Title Page

Copyright

e-EROS Editorial Board

Preface

Introduction

Selected Monographs and Reviews

A: Acrylonitrile

Allyl Ethylsulfone

Allyltributylstannane1

Allyltriphenylstannane1

4,4-Azobis(4-cyanopentanoic acid)

1,1′-Azobis-1-cyclohexanenitrile

2,2-Azobis(2,4-dimethyl-4-methoxyvaleronitrile)

2,2′-Azobis[2-(2-imidazolin-2-yl)propane] Dihydrochloride

Azobisisobutyronitrile

2,2′-Azobis(2-methylpropanimidamide) Dihydrochloride

B: Benzeneselenol1

Benzenesulfonyl Azide

1,2-Benziodoxol-3(1 H )-one Derivatives1

4,5-Bis(1,1-dimethylethyl)-6-ethoxy-2,2-dimethyl-3,7-dioxa-4-aza-6-phosphanonanoic Acid 6-Oxide

Bis(dimethylglyoximato)(methyl)(pyridine)cobalt(III)1

Bis(ethoxythiocarbonyl)sulfide

Bis[(1 R,2 S,5 R )-menthyl](phenyl)tin Hydride

Bis[4-(tridecafluorohexyl)phenyl] Diselenide

Bis(trimethylstannyl) Benzopinacolate

Bromine Azide1

Bromine Trifluoride1

(1-Bromoethenyl)chlorodimethylsilane

(Bromomethyl)chlorodimethylsilane1

N -Bromosuccinimide1

Bromotrichloromethane

t -Butyl Hydroperoxide1–3

t-Butyl Hypochlorite1

t -Butyl Hypoiodite

t -Butyl Isocyanide1,2

N - t -Butyl-1-diethylphosphono-2,2-di-methylpropyl Nitroxide

C: Carbon Monoxide1

Carbon Tetrabromide

Carbon Tetraiodide

Catecholborane1

Cerium(IV) Ammonium Nitrate1

Chlorobis(dimethylglyoximato)-(pyridine)cobalt(III)1

N -Chloro- N -cyclohexylbenzenesulfonamide1

4-(4-Chlorophenyl)-3-hydroxy-2(3 H )thiazolethione

Chromium(II) Acetate

Chromium(II) Chloride

Cobalt Salen Complexes1

Cobalt Salophen Complexes1

Copper(II) Acetate1

1,4-Cyclohexadiene

D: Decacarbonyldimanganese

(Diacetoxyiodo)benzene1–3

Dibenzoyl Peroxide1−4

Di-t-butyl Hyponitrite1

1,1-Di- t -butyl Peroxide1−3

2,2-Di( t -butylperoxy)butane

Di-t-butyl Peroxyoxalate1

N, N -Dichlorobenzenesulfonamide

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone1

Dilauroyl Peroxide

1,4:5,8-Dimethano-1,2,3,4,5,6,7,8-octahydro-9,10-dimethoxyanthracenium Hexachloroantimonate

(2,6-Dimethoxy-1-methyl-2,5-cyclohexadien-1-yl)(1,1-dimethylethyl)dimethylsilane

[2-(Dimethylamino)methyl]phenyl Dimethyltin Hydride

2,2-Dimethyl-5-[3-(diphenylstannyl)propyl]-1,3-dioxolan-4-one

Dimethyl Disulfide

5,5-Dimethyl-1-(phenylmethyl)-3-pyrazolidinone

Dimethyl[3-(1-pyrenyl)propyl]stannane

Diphenyl Diselenide1

Diphenyl Disulfide1

Diphenyl Disulfone

Diphenyl Ditelluride1

Diphenyl[2-(4-pyridyl)ethyl]tin Hydride

2,2′-Dipyridyl Disulfide N,N′-Dioxide

t -Dodecanethiol

E: Ethanesulfonyl Azide

Ethyl Difluoroiodoacetate

G: Galvinoxyl1,2

H: Hexabutyldistannane1

Hexamethyldistannane1

Hydrogen Bromide1

Hydrogen Selenide1

N-Hydroxyphthalimide

N-Hydroxypyridine-2-thione

Hypophosphorous Acid1

I: Indium

Iodine Azide1

Iodine–Nitrogen Tetroxide

2′-Iodobiphenyl-2-thiol Dimethylaluminum Complex1

Iodoform

Iodosylbenzene1

1-Iodo-2-(2,2,2-triethoxyethyl)benzene

Iron, Bis(pyridine)bis(2-pyridinecarboxylato-N1,O2)

Iron(III) Chloride1

L: Lead(IV) Acetate1

Lead(IV) Acetate–Copper(II) Acetate1

Lead(IV) Acetate–Iodine1

Lithium 4,4′-Di- t -butylbiphenylide1

Lithium 1-(Dimethylamino)naphthalenide1

Lithium Naphthalenide1

M: Manganese(III) Acetate1

Manganese(III) Acetate–Copper(II) Acetate1

Manganese(III) Acetylacetonate

Mercury(II) Oxide–Bromine1

Mercury(II) Oxide–Iodine

Methyl Acrylate

1-Methyl-2-azaadamantane N -Oxyl

N -Methylcarbazole

S -Methyl N -methyl-N -hydroxydithiocarbamate

N -Methylquinolinium Hexafluorophosphate

Methyl Thioglycolate

N: Naphthalene-1,8-diyl Bis(diphenylmethylium) Perchlorate

4-Nitrobenzenesulfenyl Chloride

o -Nitrobenzenesulfonylhydrazide

Nitroethylene1

Nitrosobenzene

Nitrosyl Chloride1

O: S-(1-Oxido-2-pyridinyl)-1,1,3,3-tetramethylthiouronium Hexafluorophosphate (HOTT)

P: 4-Pentyne-1-thiol

Peroxyacetyl Nitrate

Phenyl Chlorothionocarbonate

Phenyliodine(III) Dichloride

Phenylsulfonylethylene1

Phosphinic Acid, Alkyl Esters

Polymethylhydrosiloxane (PMHS)

Potassium O-Ethyl Xanthate

Potassium Ferricyanide1

3-Pyridinesulfonyl Azide

2-Pyridinethiol

S: Samarium(II) Iodide1

Se-Phenyl p-tolueneselenosulfonate1

Sodium Anthracenide

Sodium Bis(dimethylglyoximato)-(pyridine)cobaltate1

Sodium Hypophosphite

Sodium Naphthalenide

Sulfuryl Chloride

T: 2,2,6,6-Tetramethylpiperidin-1-oxyl1

Tetraphenyldiphosphine

1,1,2,2-Tetraphenyldisilane

Tetrathiafulvalene

1,1′-Thiocarbonylbis(1H-benzotriazole)

1,1′-Thiocarbonyldiimidazole1

Thionocarbonates1

Thiophenol

Thiophosgene1

Titanium(III) Chloride

O - p -Tolyl Chlorothioformate

Tri( t -butoxy)silanethiol

Tri- n -butyl(iodoacetoxy)stannane1

Tri- n -butylstannane1

Triethylborane

Triethylsilane1

m -Trifluoromethylbenzoyl Chloride

α,α,α-Trifluorotoluene

Triisopropylsilanethiol

Trimethylstannane1

Triphenylbismuthine1

Triphenylsilane

Triphenylstannane1

Tris(2-perfluorohexylethyl)tin Hydride

Tris(phenylthio)phosphine

Tris(trimethylsilyl)silane1

Trityl Thionitrite

X: Xenon(II) Fluoride1

Y: Ytterbium(II) Chloride1

Ytterbium(III) Trifluoromethanesulfonate & Ytterbium(III) Trifluoromethanesulfonate Hydrate Ytterbium(III) Trifluoromethanesulfonate & Ytterbium(III) Trifluoromethanesulfonate Hydrate

V: Vanadyl Trichloride

Vitamin B121−3

List of Contributors

Reagent Formula Index

Subject Index

General Abbreviations

Other Titles in this Collection

Catalyst Components for Coupling Reactions

Edited by Gary A. Molander

ISBN 978 0 470 51811 3

Fluorine-Containing Reagents

Edited by Leo A. Paquette

ISBN 978 0 470 02177 4

Reagents for Direct Functionalization for C–H Bonds

Edited by Philip L. Fuchs

ISBN 0 470 01022 3

Reagents for Glycoside, Nucleotide, and Peptide Synthesis

Edited by David Crich

ISBN 0 470 02304 X

Reagents for High-Throughput Solid-Phase and Solution-Phase Organic Synthesis

Edited by Peter Wipf

ISBN 0 470 86298 X

Chiral Reagents for Asymmetric Synthesis

Edited by Leo A. Paquette

ISBN 0 470 85625 4

Activating Agents and Protecting Groups

Edited by Anthony J. Pearson and William R. Roush

ISBN 0 471 97927 9

Acidic and Basic Reagents

Edited by Hans J. Reich and James H. Rigby

ISBN 0 471 97925 2

Oxidizing and Reducing Agents

Edited by Steven D. Burke and Rick L. Danheiser

ISBN 0 471 97926 0

Reagents, Auxiliaries and Catalysts for C–C Bond Formation

Edited by Robert M. Coates and Scott E. Denmark

ISBN 0 471 97924 4

e-EROS

For access to information on all the reagents covered in the Handbooks of Reagents for Organic Synthesis, and many more, subscribe to e-EROS on the Wiley Interscience website. A database is available with over 200 new entries and updates every year. It is fully searchable by structure, substructure and reaction type and allows sophisticated full text searches. http://www.mrw.interscience.wiley.com/eros/

This edition first published 2008

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Library of Congress Cataloging-in-Publication Data

Handbook of reagents for organic synthesis.

p.cm

Includes bibliographical references.

Contents: [1] Reagents, auxiliaries and catalysts for C–C bond formation / edited by Robert M. Coates and Scott E. Denmark [2] Oxidizing and reducing agents / edited by Steven D. Burke and Riek L. Danheiser [3] Acidic and basic reagents / edited by Hans J. Reich and James H. Rigby [4] Activating agents and protecting groups / edited by Anthony J. Pearson and William R. Roush [5] Chiral reagents for asymmetric synthesis / edited by Leo A. Paquette [6] Reagents for high-throughput solid-phase and solution-phase organic synthesis / edited by Peter Wipf [7] Reagents for glycoside, nucleotide and peptide synthesis / edited by David Crich [8] Reagents for direct functionalization of C–H bonds/edited by Philip L. Fuchs [9] Fluorine-Containing Reagents/edited by Leo A. Paquette [10] Catalyst Components for Coupling Reactions / edited by Gary A. Molander [11] Reagents for Radical and Radical Ion Chemistry/edited by David Crich

ISBN 0-471-97924-4 (v. 1)ISBN 0-471-97926-0 (v. 2)ISBN 0-471-97925-2 (v. 3)ISBN 0-471-97927-9 (v. 4)ISBN 0-470-85625-4 (v. 5)ISBN 0-470-86298-X (v. 6)ISBN 0-470-02304-X (v. 7)ISBN 0-470-01022-3 (v. 8)ISBN 978-0-470-02177-4 (v. 9)ISBN 978-0-470-51811-3 (v.10)ISBN 978-0-470-06536-5 (v. 11)

1. Chemical tests and reagents.

2. Organic compounds-Synthesis.

QD77.H37 1999

98-53088

547'.2 dc 21

CIP

A catalogue record for this book is available from the British Library.

ISBN 13: 978-0-470-06536-5

e-EROS Editorial Board

Editor-in-Chief

Leo A. Paquette

The Ohio State University, Columbus, OH, USA

Executive Editors

David Crich

Wayne State University, Detroit, MI, USA

Philip L. Fuchs

Purdue University, West Lafayette, IN, USA

Gary A. Molander

University of Pennsylvania, Philadelphia, PA, USA

Preface

As stated in its Preface, the major motivation for our undertaking publication of the Encyclopedia of Reagents for Organic Synthesis was ‘to incorporate into a single work a genuinely authoritative and systematic description of the utility of all reagents used in organic chemistry.’ By all accounts, this reference compendium succeeded admirably in approaching this objective. Experts from around the globe contributed many relevant facts that define the various uses characteristic of each reagent. The choice of a masthead format for providing relevant information about each entry, the highlighting of key transformations with illustrative equations, and the incorporation of detailed indexes serve in tandem to facilitate the retrieval of desired information.

Notwithstanding these accomplishments, the editors came to recognize that the large size of this eight-volume work and its cost of purchase often deterred the placement of copies of the Encyclopedia in or near laboratories where the need for this type of information is most critical. In an effort to meet this demand in a cost-effective manner, the decision was made to cull from the major work that information having the highest probability for repeated consultation and to incorporate the same into a set of handbooks. The latter would also be purchasable on a single unit basis.

The ultimate result of these deliberations was the publication of the Handbook of Reagents for Organic Synthesis, the first four volumes of which were published in 1999:

Reagents, Auxiliaries and Catalysts for C–C Bond FormationEdited by Robert M. Coates and Scott E. Denmark

Oxidizing and Reducing AgentsEdited by Steven D. Burke and Rick L. Danheiser

Acidic and Basic ReagentsEdited by Hans J. Reich and James H. Rigby

Activating Agents and Protecting GroupsEdited by Anthony J. Pearson and William R. Roush

Since then, the fifth, sixth, seventh, eighth, ninth and tenth members of this series listed below have made their appearance:

Chiral Reagents for Asymmetric SynthesisEdited by Leo A. Paquette

Reagents for High-Throughput Solid-Phase and Solution-Phase Organic SynthesisEdited by Peter Wipf

Reagents for Glycoside, Nucleotide, and Peptide SynthesisEdited by David Crich

Reagents for Direct Functionalization of C–H BondsEdited by Philip L. Fuchs

Fluorine-Containing ReagentsEdited by Leo A. Paquette

Catalyst Components for Coupling ReactionsEdited by Gary A. Molander

Each of the volumes contain a selected compilation of those entries from the original Encyclopedia that bear on the specific topic. The coverage of the last six handbooks also extends to the electronic sequel e-EROS. Ample listings can be found to functionally related reagents contained in the original work. For the sake of current awareness, references to recent reviews and monographs have been included, as have relevant new procedures from Organic Syntheses.

The present volume entitled Reagents for Radical and Radical Ion Chemistry constitutes the eleventh entry in a continuing series of utilitarian reference works. As with its predecessors, this handbook is intended to be an affordable, enlightening compilation that will hopefully find its way into the laboratories of all practicing synthetic chemists. Every attempt has been made to be of the broadest possible relevance and it is hoped that our many colleagues will share in this opinion.

Leo A. PaquetteDepartment of ChemistryThe Ohio State UniversityColumbus, OH, USA

Introduction

In the hands of the cognoscenti, radicals and their charged counterparts, the radical ions have long left behind their image as highly reactive uncontrollable intermediates unsuitable for application in fine chemical synthesis. Nowhere is this more apparent than in the area of stereoselective radical reactions that, as recently as the mid 1980s, were considered nothing more than a pipe dream, but that, with improved methods for radical generation, rapidly evolved within the space of a few years sufficiently to warrant publication of dedicated review articles and books. Indeed, the stereoselectivity of well-planned radical reactions is now such that it can equal and even surpass that of more widely appreciated two-electron systems. Unfortunately, it remains the case that most undergraduate organic chemistry textbooks still introduce budding chemists to radical reactions through the chlorination of methane, and so convey the general impression of a complex and unselective chemistry. Against this background, it is hoped that the reagents collected in this handbook will serve to illustrate the variety of transformations that may be readily achieved through radical and radical ion chemistry and help at least a proportion of practicing organic chemists overcome whatever remaining reluctance they may have to the application of radical chemistry in their synthetic schemes.

The success of modern radical chemistry has been achieved at the hands of numerous practitioners of the art whose dedication has resulted in the development of many of the reagents featured here. However, it is important to acknowledge that modern radical chemistry is built on a very extensive physical organic foundation and on the pioneering work of many individuals when the field was much less popular than today. Accordingly, it is fitting and appropriate that the list of selected monographs and review articles with which this handbook opens begins with a section on general and physical organic aspects before moving onto the chemistry of radical anions, then radial cations, and finally neutral radicals. Some of the monographs and reviews selected for these lists can no longer be considered recent, nevertheless they remain veritable treasure troves of little known underexploited processes waiting to be rediscovered and developed and it is for this reason that they are included here. The unbalanced division of the material, both in the lists of monographs and reviews and in the reagents themselves, with a heavy emphasis on the chemistry of neutral radicals, generally reflects the state of the art with respect to current applications in synthesis. It is to be hoped that this imbalance will be redressed as improved methods for the controlled generation of radical anions and cations become available.

Of the reagents featured in this volume, approximately one third are taken from the Encyclopedia of Reagents for Organic Synthesis (EROS), published in 1995. Many of these are classical reagents in the field whose principal use has not changed in the intervening period. The remainder, and indeed the bulk, of the entries are divided approximately equally between completely new articles and updated versions of original EROS articles taking into account recent developments, written by experts in the field for the continually expanding online encyclopedia (e-EROS). The main sequence of reagents in this volume is alphabetical in keeping with the EROS and e-EROS format.

It is hoped that this handbook will serve as a useful resource to synthetic chemists and to stimulate the ever wider use of radical and radical ions in synthetic organic chemistry.

David CrichDepartment of ChemistryWayne State UniversityDetroit, MI, USA