@jgi6aYZg &.%'Ã&.*CdWZaEg^oZ!&.*% :YjVgY7jX]cZg &-+%Ã&.&, CdWZaEg^oZ!&.%, 6Yda[kdc7VZnZg &-(*Ã&.&, CdWZaEg^oZ!&.%* :a^Vh?VbZh8dgZn &.'-Ã CdWZaEg^oZ!& % 9ZgZ`=#G#7Vgidc &.&-Ã& CdWZaEg^oZ!&.+ DiidEVja=ZgbVcc9^Zah &-,+Ã&.*) CdWZaEg^oZ!&.*% Name Reactions Jie Jack Li Name Reactions A Collection of Detailed Reaction Mechanisms Third Expanded Edition 123 Jie Jack Li, Ph.D Pfizer Global Research and Development Chemistry Department 2800 Plymouth Road Ann Arbor, MI 48105 USA e-mail: jack.li@pfizer.com 3rd expanded ed ISBN-10 3-540-30030-9 Springer Berlin Heidelberg New York ISBN-13 978-3-540-30030-4 Springer Berlin Heidelberg New York e-ISBN 3-540-30031-7 ISBN-10 3-540-40203-9 2nd ed Springer Berlin Heidelberg New York Library of Congress Control Number: 2006925628 This work is subject to copyright All rights reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer Violations are liable for prosecution under the German Copyright Law Springer is a part of Springer Science+Business Media springer.com © Springer-Verlag Berlin Heidelberg 2003, 2006 Printed in Germany The use of general descriptive names, registered names, trademarks, etc in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use Typesetting: By the Author Production: LE-TEX, Jelonek, Schmidt & Vöckler GbR, Leipzig Coverdesign: KünkelLopka, Heidelberg Printed on acid-free paper 2/3100 YL – Dedicated to Professor E J Corey Foreword I don't have my name on anything that I don't really –Heidi Klum Can the organic chemists associated with so-called “Named Reactions” make the same claim as supermodel Heidi Klum? Many scholars of chemistry not hesitate to point out that the names associated with “name reactions” are often not the actual inventors For instance, the Arndt-Eistert reaction has nothing to with either Arndt or Eistert, Pummerer did not discover the “Pummerer” rearrangement, and even the famous Birch reduction owes its initial discovery to someone named Charles Wooster (first reported in a DuPont patent) The list goes on and on… But does that mean we should ignore, boycott, or outlaw “named reactions”? Absolutely not The above examples are merely exceptions to the rule In fact, the chemists associated with name reactions are typically the original discoverers, contribute greatly to its general use, and/or are the first to popularize the transformation Regardless of the controversial history underlying certain named reactions, it is the students of organic chemistry who benefit the most from the cataloging of reactions by name Indeed, it is with education in mind that Dr Jack Li has masterfully brought the chemical community the latest edition of Name Reactions It is clear why this beautiful treatise has rapidly become a bestseller within the chemical community The quintessence of hundreds of named reactions is encapsulated in a concise format that is ideal for students and seasoned chemists alike Detailed mechanistic and occasionally even historical details are given for hundreds of reactions along with key references This “must-have” book will undoubtedly find a place on the bookshelves of all serious practitioners and students of the art and science of synthesis Phil S Baran La Jolla, March 2006 Preface Confucius said: “Reviewing old knowledge while learning new old knowledge, is that not, after all, a pleasure?” Indeed, name reactions are not only the fruit of pioneering organic chemists, but also our contemporaries whose combined discoveries have resulted in organic chemistry today Since publication of this book, Barry Sharpless and Ryoji Noyori, whose name reactions have been included since the first edition, went on to win the Nobel Prizes in 2001 Recently, Richard Schrock, Robert Grubbs, and Yves Chauvin shared the 2005 Nobel Prize in chemistry for their contributions to metathesis, a name reaction that has been also included since the first edition Therefore, I intend to keep up with the new developments in the field of organic chemistry while retaining the collection of name reactions that have withheld test of time The third edition contains major improvements over the previous two editions I have updated references Each reaction is now supplemented with two to three representative examples in synthesis to showcase its synthetic utility As Emil Fischer stated: “Science is not an abstraction; but as a product of human endeavor it is inseparably bound up in its development with the personalities and fortunes of those who dedicate themselves to it.” To that end, I added biographical sketches for most of the chemists who discovered or developed those name reactions Furthemore, I have significantly beefed up the subject index to help the reader navigate the book more easily In preparing this manuscript, I have incurred many debts of gratitude to Prof Reto Mueller of Switzerland, Prof Robin Ferrier of New Zealand, and Prof James M Cook of the University of Wisconsin, Milwaukee; Dr Yike Ni of California Institute of Technology, and Dr Shengping Zheng of Columbia University for invaluable suggestions I also wish to thank Dr Gilles Chambournier, Prof Phil S Baran of Scripps Research Institute and his students, Narendra Ambhaikar, Ben Hafensteiner, Carlos Guerrero, and Dan O’Malley, Prof Brian M Stoltz of California Institute of Technology and his students, Kevin Allan, Daniel Caspi, David Ebner, Andrew Harned, Shyam Krishnan, Michael Krout, Qi Charles Liu, Sandy Ma, Justin Mohr, John Phillips, Jennifer Roizen, Brinton Seashore-Ludlow, Nathaniel Sherden, Jennifer Stockdill, and Carolyn Woodroofe for proofreading the final draft of the manuscript Their knowledge and time have tremendously enhanced the quality of this book Any remaining errors are, of course, solely my own responsibility I welcome your critique Jack Li Ann Arbor, Michigan, March 2006 Table of Contents Abbreviations XVIII Alder ene reaction Aldol condensation Algar–Flynn–Oyamada reaction Allan–Robinson reaction Appel reaction 10 Arndt–Eistert homologation 12 Baeyer–Villiger oxidation 14 Baker–Venkataraman rearrangement 16 Bamberger rearrangement 18 Bamford–Stevens reaction 20 Barbier coupling reaction 22 Bargellini reaction 24 Bartoli indole synthesis 26 Barton radical decarboxylation 28 Barton–McCombie deoxygenation 30 Barton nitrite photolysis 32 Barton–Zard reaction 34 Batcho–Leimgruber indole synthesis 36 Baylis–Hillman reaction 39 Beckmann rearrangement 41 Beirut reaction 43 Benzilic acid rearrangement 45 Benzoin condensation 47 Bergman cyclization 49 Biginelli pyrimidone synthesis 51 Birch reduction 53 Bischler–Möhlau indole synthesis 55 Bischler–Napieralski reaction 57 Blaise reaction 59 Blanc chloromethylation 61 Blum aziridine synthesis 63 Boekelheide reaction 65 Boger pyridine synthesis 67 Borch reductive amination 69 Borsche–Drechsel cyclization 71 Boulton–Katritzky rearrangement 73 Bouveault aldehyde synthesis 75 Bouveault–Blanc reduction 77 Boyland–Sims oxidation 79 Bradsher reaction 81 Brook rearrangement 83 Brown hydroboration 85 XII Bucherer carbazole synthesis 87 Bucherer reaction 90 Bucherer–Bergs reaction 92 Büchner–Curtius–Schlotterbeck reaction 94 Büchner method of ring expansion 96 Buchwald–Hartwig C–N bond and C–O bond formation reactions 98 Burgess dehydrating reagent 100 Cadiot–Chodkiewicz coupling 102 Camps quinolinol synthesis 104 Cannizzaro dispropotionation 107 Carroll rearrangement 109 Castro–Stephens coupling 112 Chan alkyne reduction 114 Chan–Lam coupling reaction 116 Chapman rearrangement 118 Chichibabin pyridine synthesis 120 Chugaev reaction 123 Ciamician–Dennsted rearrangement 125 Claisen condensation 127 Claisen isoxazole synthesis 129 Claisen rearrangement 131 Abnormal Claisen rearrangement 133 Eschenmoser–Claisen amide acetal rearrangement 135 Ireland–Claisen (silyl ketene acetal) rearrangement 137 Johnson–Claisen (orthoester) rearrangement 139 Clemmensen reduction 141 Combes quinoline synthesis 144 Conrad–Limpach reaction 147 Cope elimination reaction 149 Cope rearrangement 151 Oxy-Cope rearrangement 152 Anionic oxy-Cope rearrangement 153 Corey–Bakshi–Shibata (CBS) reduction 154 CoreyChaykovsky reaction 157 Corey–Fuchs reaction 160 Corey–Kim oxidation 162 Corey–Nicolaou macrolactonization 164 Corey–Seebach dithiane reaction 166 Corey–Winter olefin synthesis 168 Criegee glycol cleavage 171 Criegee mechanism of ozonolysis 173 Curtius rearrangement 175 Dakin oxidation 177 Dakin–West reaction 179 Danheiser annulation 181 Darzens glycidic ester condensation 183 XIII Davis chiral oxaziridine reagent 185 Delépine amine synthesis 187 de Mayo reaction 189 Demjanov rearrangement 191 Tiffeneau–Demjanov rearrangement 193 Dess–Martin oxidation 195 Dieckmann condensation 197 Diels–Alder reaction 199 Dienone–phenol rearrangement 202 Di-S-methane rearrangement 204 Doebner quinoline synthesis 206 Dötz reaction 208 Dowd–Beckwith ring expansion 210 ErlenmeyerPlöchl azlactone synthesis 212 Eschenmoser–Tanabe fragmentation 214 Eschweiler–Clarke reductive alkylation of amines 216 Evans aldol reaction 218 Favorskii rearrangement and quasi-Favorskii rearrangement 220 Feist–Bénary furan synthesis 222 Ferrier carbocyclization 224 Ferrier glycal allylic rearrangement 227 Fiesselmann thiophene synthesis 230 Fischer indole synthesis 233 Fischer oxazole synthesis 235 Fleming–Tamao oxidation 237 TamaoKumada oxidation 239 Friedel–Crafts reaction 240 Friedländer quinoline synthesis 243 Fries rearrangement 245 Fukuyama amine synthesis 247 Fukuyama reduction 249 Gabriel synthesis 251 Ing–Manske procedure 253 Gabriel–Colman rearrangement 255 Gassman indole synthesis 257 Gattermann–Koch reaction 259 Gewald aminothiophene synthesis 261 Glaser coupling 263 Eglinton coupling 265 Gomberg–Bachmann reaction 267 Gould–Jacobs reaction 269 Grignard reaction 271 Grob fragmentation 273 Guareschi–Thorpe condensation 275 Hajos–Wiechert reaction 277 Haller–Bauer reaction 279 .. .Name Reactions Jie Jack Li Name Reactions A Collection of Detailed Reaction Mechanisms Third Expanded Edition 123... controversial history underlying certain named reactions, it is the students of organic chemistry who benefit the most from the cataloging of reactions by name Indeed, it is with education in mind... latest edition of Name Reactions It is clear why this beautiful treatise has rapidly become a bestseller within the chemical community The quintessence of hundreds of named reactions is encapsulated