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Advanced Organic Chemistry Advanced Organic • t FOURTH CheffilS fY EDITION Part B: Reactions and Synthesis Advanced Organic Chemistry PART A: Structure and Mechanisms PART B: Reactions and Synthesis Advanced Organic • t FOURTH ChemlS ry EDITION Part B: Reactions and Synthesis FRANCIS A. CAREY and RICHARD J. SUNDBERG University of Virginia Charlottesville, Virginia ~Springer Library of Congress Cataloging-in-Publication Data Carey, Francis A., 1937- Advanced organic chemistry/Francis A. Carey and Richard J. Sundberg.-4th ed. p. em. Includes bibliographical references and index. Contents: pt. B. Reactions and synthesis I. Sundberg, Richard J., 1938- II. Title. QD251.2 .C36 2000 547-dc21 00-059652 Library of Congress Cataloging-in-Publication Data Carey, Francis A., 1937- Advanced organic chemistry/Francis A. Carey and Richard ). Sundberg.-4th ed. p.cm. Includes bibliographical references and index. Contents: pt. B. Reactions and synthesis I. Sundberg, Richard)., 1938- II. Title. QD251.2 .C36 2000 547-dc21 00-059652 A C.I.P. record for this book is available from the Library of Congress ISBN 978-3-662-38652-1 ISBN 978-3-662-39510-3 (eBook) DOI 10.1007/978-3-662-39510-3 © 2001,1990,1984,1977 Springer Science+ Business Media New York Originally published by Springer Science Business Media, Inc. in 2001 All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transmit­ ted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher. (Springer Science+Business Media, LLC). The front cover shows the key orbital interactions in the Diels-Alder reaction. The highest-occupied molecular orbital (HOMO) of 1,3-butadiene and the lowest-unoccupied molecular orbital (LUMO) of ethylene overlap in phase with one another allowing the reaction to occur in a single step. 10 9 8 7 6 5 4 3 springeronline.com Preface to the Fourth Edition Part B emphasizes the most important reactions used in organic synthesis. The material is organized by reaction type. Chapters 1 and 2 discuss the alkylation, conjugate addition and carbonyl addition/condensation reactions of enolates and other carbon nucleophiles. Chapter 3 covers the use of nucleophilic substitution, both at saturated carbon and at carbonyl groups, in functional group of interconversions. Chapter 4 discusses electrophilic additions to alkenes and alkynes, including hydroboration. Chapter 5 discusses reduction reactions, emphasizing alkene and carbonyl-group reductions. Concerted reactions, especially Diels-Alder and other cycloadditions and sigmatropic rearrangements, are considered in Chapter 6. Chapters 7, 8, and 9 cover organometallic reagents and intermediates in synthesis. The main-group elements lithium and magnesium as well as zinc are covered in Chapter 7. Chapter 8 deals with the transition metals, especially copper, palladium, and nickel. Chapter 9 discusses synthetic reactions involving boranes, silanes, and stannanes. Synthetic reactions which involve highly reactive intermediates-carboca­ tions, carbenes, and radicals-are discussed in Chapter 10. Aromatic substitution by both e1ectrophilic and nucleophilic reagents is the topic of Chapter 11. Chapter 12 discusses the most important synthetic procedures for oxidizing organic compounds. In each of these chapters, the most widely used reactions are illustrated by a number of specific examples of typical procedures. Chapter 13 introduces the concept of synthetic planning, including the use of protective groups and synthetic equivalents. Multistep syntheses are illustrated with several syntheses of juvabione, longifolene, Prelog-Djerassi lactone, Taxol, and epothilone. The chapter concludes with a discussion of solid-phase synthesis and its application in the synthesis of polypeptides and oligonucleotides, as well as to combina­ torial synthesis. The control of reactivity to achieve specific syntheses is one of the overarching goals of organic chemistry. In the decade since the publication of the third edition, major advances have been made in the development of efficient new methods, particularly catalytic processes, and in means for control of reaction stereochemistry. For example, the scope and efficiency of palladium- catalyzed cross coupling have been greatly improved by optimization of catalysts by ligand modification. Among the developments in stereocontrol are catalysts for enantioselective reduction of ketones, improved methods for control of the v Vl stereoselectivity of Diels-Alder reactions, and improved catalysts for enantioselective hydroxylation and epoxidation of alkenes. PREFACE TO THE FOURTH EDmON This volume assumes a level of familiarity with structural and mechanistic concepts comparable to that in the companion volume, Part A, Structure and Mechanisms. Together, the two volumes are intended to provide the advanced undergraduate or beginning graduate student in chemistry a sufficient foundation to comprehend and use the research literature in organic chemistry. Contents of Part B Chapter 1. Alkylation of Nucleophilic Carbon Intermediates .......... 1.1. Generation of Carbanions by Deprotonation .................... 1.2. Regioselectivity and Stereoselectivity in Enolate Formation .......... 5 1.3. Other Means of Generating Enolates . 10 1.4. Alkylation of Enolates .................................. 11 1.5. Generation and Alkylation of Dianions ....................... 20 1.6. Medium Effects in the Alkylation of Enolates ................... 20 1.7. Oxygen versus Carbon as the Site of Alkylation ................. 23 1.8. Alkylation of Aldehydes, Esters, Amides, and Nitriles ............. 28 1.9. The Nitrogen Analogs of Enols and Enolates-Enamines and Imine Anions ............................................. 31 1.10. Alkylation of Carbon Nucleophiles by Conjugate Addition .......... 39 General References ................................... 47 Problems 47 Chapter 2. Reaction of Carbon Nucleophiles with Carbonyl Groups . 57 2.1. Aldol Addition and Condensation Reactions. 57 2.1.1. The General Mechanism . 57 2.1.2. Mixed Aldol Condensations with Aromatic Aldehydes . 60 2.1.3. Control of Regiochemistry and Stereochemistry of Mixed Aldol Reactions of Aliphatic Aldehydes and Ketones . 62 2.1.4. Intramolecular Aldol Reactions and the Robinson Annulation . 89 2.2. Addition Reactions of !mines and Iminium Ions . 96 2.2.1. The Mannich Reaction. 96 2.2.2. Amine-Catalyzed Condensation Reactions. 100 2.3. Acylation of Carbanions. 101 Vll viii 2.4. The Wittig and Related Reactions of Phosphorus-Stabilized Carbon Nucleophiles . Ill CONTENTS OF PART B 2.5. Reactions of Carbonyl Compounds with oc-Trimethylsilylcarbanions. 120 2.6. Sulfur Ylides and Related Nucleophiles . 122 2.7. Nucleophilic Addition--Cyclization. 127 General References . 128 Problems . 128 Chapter 3. Functional Group Interconversion by Nucleophilic Substitution . 141 3.1. Conversion of Alcohols to Alkylating Agents . 141 3 .1.1. Sulfonate Esters . 141 3.1.2. Halides. 142 3.2. Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon . 147 3.2.1. General Solvent Effects ............................. 147 3.2.2. Nitrites ........................................ 150 3.2.3. Azides ........................................ 150 3.2.4. Oxygen Nucleophiles .............................. 152 3.2.5. Nitrogen Nucleophiles .............................. 155 3.2.6. Sulfur Nucleophiles ............................... 158 3.2.7. Phosphorus Nucleophiles ............................ 158 3.2.8. Summary of Nucleophilic Substitution at Saturated Carbon ..... 159 3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters ... 159 3.4. Interconversion of Carboxylic Acid Derivatives .................. 164 3.4.1. Preparation of Reactive Reagents for Acylation ............. 166 3.4.2. Preparation of Esters .......................... : . ... 172 3.4.3. Preparation of Amides.............................. 172 Problems 180 Chapter 4. Electrophilic Additions to Carbon-Carbon Multiple Bonds . 191 4.1. Addition of Hydrogen Halides.. 191 4.2. Hydration and Other Acid-Catalyzed Additions of Oxygen Nucleophiles . 195 4.3. Oxymercuration . 196 4.4. Addition of Halogens to Alkenes. 200 4.5. Electrophilic Sulfur and Selenium Reagents. 209 4.6. Addition of Other Electrophilic Reagents . 216 4.7. Electrophilic Substitution Alpha to Carbonyl Groups. 216 4.8. Additions to Allenes and Alkynes . 222 4.9. Addition at Double Bonds via Organoborane Intermediates . 226 4.9.1. Hydroboration. 226 4.9.2. Reactions of Organoboranes. 232 4.9.3. Enantioselective Hydroboration. 236 4.9.4. Hydroboration of Alkynes . 239 General References . 240 IX Problems .......................................... 241 CONTENTS OF PART B Chapter 5. Reduction of Carbonyl and Other Functional Groups ....... 249 5.1. Addition of Hydrogen .................................. 249 5.1.1. Catalytic Hydrogenation. 249 5.1.2. Other Hydrogen-Transfer Reagents .................... 262 5.2. Group III Hydride-Donor Reagents .......................... 262 5.2.1. Reduction of Carbonyl Compounds .................... 262 5.2.2. Stereoselectivity of Hydride Reduction .................. 273 5.2.3. Reduction of Other Functional Groups by Hydride Donors .... 280 5.3. Group IV Hydride Donors ................................ 286 5.4. Hydrogen-Atom Donors ................................. 288 5.5. Dissolving-Metal Reductions .............................. 290 5.5 .1. Addition of Hydrogen ............................. 292 5.5.2.
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