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Advanced Organic Synthesis
METHODS AND TECHNIQUES

RICHARD S. MONSON
DEPARTMENT OF CHEMISTRY CALIFORNIA STATE COLLEGE, HAYWARD HAYWARD, CALIFORNIA

ACADEMIC PRESS New York and London

COPYRIGHT © 1971, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORN BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY OTHER MEANS, WITHOUT WRITTEN PERMISSIONFROM THE PUBLISHERS.

ACADEMIC PRESS, INC.

Ill Fifth Avenue, New York, New York 10003

United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD.
Berkeley Square House, London WlX 6BA

LIBRARY OF CONGRESS CATALOG CARD NUMBER: 75-165531

PRINTED IN THE UNITED STATES OF AMERICA

Contents
Preface xi

I. FUNCTIONAL GROUP MODIFICATIONS 1. Chemical Oxidations
I. II. III. IV.V. VI. VII. VIII. IX. X. XI. Chromium Trioxide Oxidation Periodate-Permanganate Cleavage of Olefins Free Radical Oxidation of an Allylic Position Epoxidation of Olefins Baeyer-Villiger Oxidation of Ketones Lead Tetraacetate Oxidation of Cycloalkanols Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime Oxidation of Ethers to Esters Partial Oxidation of an Aliphatic Side ChainBisdecarboxylation with Lead Tetraacetate Oxidation with Selenium Dioxide References 3 5 7 8 9 11 11 12 13 14 15 16

2.
I. II. III. IV.

Hydride and Related Reductions
Reduction by Lithium Aluminum Hydride Mixed Hydride Reduction Reduction with Iridium-Containing Catalysts Reduction of Conjugated Alkenes with Chromium (H) Sulfate References 18 20 22 23 24

3. Dissolving Metal Reductions
I. II. III. IV.V. Reduction by Lithium-Amine Reduction by Lithium-Ethylenediamine Reduction of a,/MJnsaturated Ketones by Lithium-Ammonia Reduction of a,/9-Unsaturated Ketones in Hexamethylphosphoric Triamide Reduction of an a,/?-Unsaturated y-Diketone with Zinc References 25 26 27 28 29 30

. . . .

VI

CONTENTS

4. Hydroboration
I. Hydroboration of Olefins as a Route to Alcohols II. SelectiveHydroborations Using Bis(3-methyl-2-butyl)borane (BMB) III. Purification of a Mixture of J 9 - 10 - and J1(9)-Octalins References 32 35 37 38

5. Catalytic Hydrogenation
I. II. III. IV. V. Hydrogenation over Platinum Catalyst Low-Pressure Hydrogenation of Phenols over Rhodium Catalysts c/j-4-Hydroxycyclohexanecarboxylic Acid from /?-Hydroxybenzoic Acid 3-Isoquinuclidone from/7-Aminobenzoic AcidHomogeneous Catalytic Hydrogenation References 39 40 41 42 43 44

6. The Introduction of Halogen
I. II. III. IV. V. Halides from Alcohols by Triphenylphosphine—Carbon Tetrahalide Halides from Alcohols and Phenols by Triphenylphosphine Dihalide Allylic and Benzylic Bromination with W-Bromosuccinimide a-Bromination of Ketones and Dehydrobromination Stereospecific Synthesis of /ra/w-4-HalocyclohexanolsReferences 45 46 48 49 51 52

7. Miscellaneous Elimination, Substitution, and Addition Reactions
I. II. III. IV. V. VI. VII. VIII. IX. X. XI. XII. Methylenecyclohexane by Pyrolysis of an Amine Oxide The Wolff-Kishner Reduction Dehydration of 2-Decalol Boron Trifluoride Catalyzed Hydrolysis of Nitriles Bridged Sulfides by Addition of Sulfur Dichloride to Dienes Methylation by DiazomethaneOxymercuration: A Convenient Route to Markovnikov Hydration of Olefins . Esterification of Tertiary Alcohols Ketalization Half-EsterificationofaDiol Substitution on Ferrocene Demethylation of Aryl Methyl Ethers by Boron Tribromide References 54 55 56 56 57 58 60 62 63 64 65 66 67

. . .

CONTENTS

VlI

II.

SKELETAL MODIFICATIONS

8. The Diels-Alder Reaction
I. II. III. IV. V.3,6-Diphenyl-4,5-cyclohexenedicarboxylic Anhydride ........... Reactions with Butadiene .................. Catalysis by Aluminum Chloride ................ Generation of Dienes from Diones ................ Reactions with Cyclopentadiene ................. References ....................... 71 72 74 75 77 79

9.

Enamines as Intermediates
Preparation of the Morpholine Enamine of Cyclohexanone ............
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