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The Diels±Alder Reaction The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) The Diels±Alder Reaction The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) The Diels±Alder Reaction Selected Practical Methods Francesco Fringuelli UniversitaÁ degli Studi di Perugia, Italy Aldo Taticchi UniversitaÁ degli Studi di Perugia, Italy The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) Copyright # 2002 John Wiley & Sons,Ltd Baffins Lane,Chichester, West Sussex,PO19 1UD,England National 01243 779777 International -44) 1243 779777 e-mail -for orders and customer service enquiries): [email protected] Visit our Home Page on http://www.wiley.co.uk or http://www.wiley.com All Rights Reserved. No part of this publication may be reproduced,stored in a retrieval system,or transmitted,in any form or by any means,electronic,mechanical,photocopying,recording, scanning or otherwise,except under the terms of the Copyright Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd,90 Tottenham Court Road,London W1P 0LP,UK,without the permission in writing of the Publisher. Other Wiley Editorial Offices John Wiley & Sons,Inc.,605 Third Avenue, New York,NY 10158±0012,USA WILEY-VCH Verlag GmbH Pappelallee 3,D-69469 Weinheim,Germany John Wiley & Sons Australia,Ltd 33 Park Road,Milton,Queensland 4064,Australia John Wiley & Sons -Canada) Ltd,22 Worcester Road Rexdale,Ontario,M9W 1L1,Canada John Wiley & Sons -Asia) Pte Ltd,2 Clementi Loop #02±01, Jin Xing Distripark,Singapore 129809 Library of Congress Cataloging-in-Publication Data Fringuelli,Francesco. The Diels Alder reaction: selected practical methods / Francesco Fringuelli,Aldo Taticchi. p. cm. Includes bibliographical references and index. ISBN 0-471-80343-X -acid-free paper) 1. Diels-Alder reaction. I. Taticchi,Aldo. II. Title. QD281.R5 F75 2002 5470.2Ðdc21 2001024910 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0-471-80343-X Typeset in 10/12pt Times by Kolam Information Services Pvt. Ltd,Pondicherry,India. Printed and bound in Great Britain by Biddles Ltd,Guildford,Surrey. This book is printed on acid-free paper responsibly manufactured from sustainable forestry,in which at least two trees are planted for each one used for paper production. to our wives The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) Contents Preface xi Abbreviations and Acronyms xiii 1 Diels±Alder Reaction: General Remarks 1 1.1 Introduction 1 1.2 Diene and Dienophile 3 1.3 Pericyclic Diels±Alder Reaction 4 1.4 Ionic and Radical Diels±Alder Reactions 5 1.5 Regiochemistry 10 1.6 Stereochemistry 12 1.7 Retro Diels±Alder Reaction 15 1.8 Homo-Diels±Alder Reaction 18 1.9 Multiple Diels±Alder Reaction 20 1.10 Theory 22 1.10.1 Reactivity and Substituent Effects 22 1.10.2 Regioselectivity 23 1.10.3 Stereoselectivity 24 References 25 2Thermal Diels±Alder Reaction 29 2.1 Introduction 29 2.2 Carbon Diels±Alder Reactions 29 2.2.1 Open-Chain Dienes 29 2.2.2 Cyclopentadienes and Cyclohexadienes 37 2.2.3 Heterocyclic Dienes 40 2.2.4 Outer-Ring Dienes 43 2.2.5 Inner-Outer-Ring Dienes 49 2.2.6 Across-Ring Dienes 64 2.3 Hetero-Diels±Alder Reactions 66 2.3.1 Heterodienes 66 2.3.2 Heterodienophiles 70 2.4 Intramolecular Diels±Alder Reaction 74 2.5 Outlined Diels±Alder Reactions 83 References 92 viii Contents 3 Lewis-Acid Catalyzed Diels±Alder Reaction 99 3.1 Introduction 99 3.2 Carbon Diels±Alder Reaction 100 3.2.1 Cycloadditions of Cycloalkenones 100 3.2.2 Heterocyclic Dienophiles 106 3.2.3 Rare Earth Metals and Scandium Triflates 108 3.2.4 Bulky Lewis Acids 110 3.2.5 Heterocyclic Dienes 110 3.2.6 Sulfinyl Group Containing Dienes and Dienophiles 112 3.2.7 Transition Metal-Based Catalysts 114 3.2.8 Heterogeneous Catalysis 115 3.2.9 Chiral Catalysts 116 3.3 Hetero-Diels±Alder Reaction 122 3.3.1 Normal Diels±Alder Reactions. Synthesis of Pyrones and Thiopyrans 122 3.3.2 Inverse Diels±Alder Reactions. Synthesis of Pyranes 123 3.3.3 Pyrones and Triazines as Dienes 126 3.4 Homo-Diels±Alder Reaction 126 3.5 Cationic Diels±Alder Reaction 128 3.6 Outlined Diels±Alder Reactions 130 References 138 4 Diels±Alder Reaction Facilitated by Special Physical and Chemical Methods 143 4.1 Solid-Phase Diels±Alder Reaction 143 4.1.1 Inorganic Solid-Surface Promoted Diels±Alder Reaction 143 4.1.2 Diels±Alder Reaction Using Resin-Anchored Reagents 149 4.2 Ultrasound-Assisted Diels±Alder Reaction 154 4.3 Microwave-Assisted Diels±Alder Reaction 158 4.4 Photo-Induced Diels±Alder Reaction 163 4.5 Diels±Alder Reaction in Molecular Cavities 170 4.6 Micelle-Promoted Diels±Alder Reaction 174 4.6.1 Diels±Alder Reactions of Surfactant Reagents 174 4.6.2 Micellar Catalysis 176 4.7 Biocatalyst-Promoted Diels±Alder Reaction 180 4.7.1 Proteins and Enzymes Catalysis 180 4.7.2 Antibody Catalysis 183 4.8 Brùnsted Acid-Catalyzed Diels±Alder Reaction 185 4.9 Miscellaneous Diels±Alder Reactions 190 4.10 Outlined Diels±Alder Reactions 194 References 200 Contents ix 5 High Pressure Diels±Alder Reaction 205 5.1 Introduction 205 5.2 Open-Chain Dienes 208 5.2.1 Cycloadditions with Carbodienophiles 208 5.2.2 Cycloadditions with Heterodienophiles 213 5.3 Outer-Ring Dienes 217 5.4 Inner-Outer-Ring Dienes 219 5.5 Inner-Ring Dienes 223 5.5.1 Cyclopentadienes and Cyclohexadienes 223 5.5.2 Tropones as Dienes 226 5.5.3 Furans and Thiophenes 229 5.5.4 Pyrones and Pyridones 234 5.6 Outlined Diels±Alder Reactions 237 References 246 6 Diels±Alder Reaction in Unconventional Reaction Media 251 6.1 Diels±Alder Reaction in Aqueous Medium 251 6.1.1 Uncatalyzed Diels±Alder Reaction 252 6.1.2 Catalyzed Diels±Alder Reaction 261 6.2 Diels±Alder Reaction in Non-Aqueous Polar Systems 268 6.2.1 Lithium Perchlorate±Diethyl Ether 268 6.2.2 Lithium Perchlorate±Nitromethane 273 6.2.3 Lithium Trifluoromethanesulfonimide in Acetone or Diethyl Ether 274 6.2.4 para-Chlorophenol and Ethylene Glycol 276 6.2.5 Ionic Liquids 278 6.3 Diels±Alder Reaction in Microemulsion 280 6.4 Diels±Alder Reaction in Supercritical Fluids 284 6.4.1 Diels±Alder Reaction in Supercritical Water 285 6.4.2 Diels±Alder Reaction in Supercritical Carbon Dioxide 286 6.5 Outlined Diels±Alder Reactions 289 References 297 7 Diels±Alder Reaction Compilation 301 7.1 Compilation 301 7.2 Keyword Index -Chapter 7) 325 Subject Index 331 The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) Preface The Diels-Alder reaction,probably the most widely used methodology in organic synthesis today,has contributed greatly to the development of mech- anistic and theoretical chemistry. The recent discovery of a Diels±Alderase enzyme has provided insights into the mechanism of biosynthetic cycloaddition. As a follow-up to our book Dienes in the Diels±Alder Reaction -1990) and in light of our personal experience as well as the reviews and books that have been published on this topic to date,we decided that a book collecting and describing the experimental methods that have been developed to perform the Diels±Alder reaction would be a useful tool for researchers working in organic synthesis. The first chapter presents the general aspects of the reaction; Chapters 2±6 illustrate the various methods and their applications in organic synthesis. At the end of each chapter a list of graphically abstracted Diels±Alder reactions is presented to show selected synthetic applications of the specific methodology. The discussion of the various topics is not exhaustive because our aim has been to emphasize the synthetic potential of each method. Chapter 7 reports a list of books,reviews,monographs and symposia proceedings which have appeared since 1990 and an index of keywords to help the reader find a particular paper of interest. The book is directed toward undergraduate and graduate level students,as well as to academic and industrial researchers working in organic synthesis. We are grateful to Drs Assunta Marrocchi,Oriana Piermatti and Luigi Vaccaro for their assistance with the drawings. Francesco Fringuelli Aldo Taticchi The Diels±Alder Reaction: Selected Practical Methods Edited by Francesco Fringuelli and Aldo Taticchi Copyright # 2002 John Wiley & Sons,Ltd ISBNs: 0-471-80343-X -Hardback); 0-470-84581-3 -Electronic) Abbreviations and Acronyms Ac acetyl acac acetylacetonate AIBN 2,20-azobisisobutyronitrile Ar aryl 9-BBN 9-borabicyclo-[3.3.1]-nonyl BINOL 1,10-bi-2-naphthol BLA Brùnsted Lewis acid BMIM 1-butyl-3-methylimidazolium cation Bn benzyl BOM benzyloxymethyl BP N-1-butylpyridinium cation Bu n-butyl i-Bu iso-butyl t-Bu tert-butyl Bz benzoyl CAB chiral acyloxyborane CAN ceric ammonium nitrate Cat catalyst Cat* chiral catalyst CBZ or Cbz benzyloxycarbonyl or carbobenzyloxy COD cyclooctadiene Cp cyclopentadienyl CSA camphorsulfonic acid CTAB cetyltrimethylammonium bromide Cy cyclohexyl DBU 1,8-diazabicyclo-[5.4.0]-undec-7-ene DCM dichloromethane
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