Advanced Organic Synthesis

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 PERMISSION FROM 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. 2. 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 Chain Bisdecarboxylation with Lead Tetraacetate Oxidation with Selenium Dioxide References 3 5 7 8 9 11 11 12 13 14 15 16 Hydride and Related Reductions I. II. III. IV. 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 Reduc