ebook img

Name Reactions: A Collection of Detailed Reaction Mechanisms PDF

669 Pages·2006·4.119 MB·English
Save to my drive
Quick download
Download
Most books are stored in the elastic cloud where traffic is expensive. For this reason, we have a limit on daily download.

Preview Name Reactions: A Collection of Detailed Reaction Mechanisms

(cid:64)(cid:106)(cid:103)(cid:105)(cid:21)(cid:54)(cid:97)(cid:89)(cid:90)(cid:103) (cid:58)(cid:89)(cid:106)(cid:86)(cid:103)(cid:89)(cid:21)(cid:55)(cid:106)(cid:88)(cid:93)(cid:99)(cid:90)(cid:103) (cid:38)(cid:46)(cid:37)(cid:39)(cid:195)(cid:38)(cid:46)(cid:42)(cid:45) (cid:38)(cid:45)(cid:43)(cid:37)(cid:195)(cid:38)(cid:46)(cid:38)(cid:44) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:42)(cid:37) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:37)(cid:44) (cid:54)(cid:89)(cid:100)(cid:97)(cid:91)(cid:21)(cid:107)(cid:100)(cid:99)(cid:21)(cid:55)(cid:86)(cid:90)(cid:110)(cid:90)(cid:103) (cid:58)(cid:97)(cid:94)(cid:86)(cid:104)(cid:21)(cid:63)(cid:86)(cid:98)(cid:90)(cid:104)(cid:21)(cid:56)(cid:100)(cid:103)(cid:90)(cid:110) (cid:38)(cid:45)(cid:40)(cid:42)(cid:195)(cid:38)(cid:46)(cid:38)(cid:44) (cid:38)(cid:46)(cid:39)(cid:45)(cid:195) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:37)(cid:42) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:46)(cid:37) (cid:57)(cid:90)(cid:103)(cid:90)(cid:96)(cid:21)(cid:61)(cid:35)(cid:21)(cid:71)(cid:35)(cid:21)(cid:55)(cid:86)(cid:103)(cid:105)(cid:100)(cid:99) (cid:68)(cid:105)(cid:105)(cid:100)(cid:21)(cid:69)(cid:86)(cid:106)(cid:97)(cid:21)(cid:61)(cid:90)(cid:103)(cid:98)(cid:86)(cid:99)(cid:99)(cid:21)(cid:57)(cid:94)(cid:90)(cid:97)(cid:104) (cid:38)(cid:46)(cid:38)(cid:45)(cid:195)(cid:38)(cid:46)(cid:46)(cid:46) (cid:38)(cid:45)(cid:44)(cid:43)(cid:195)(cid:38)(cid:46)(cid:42)(cid:41) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:43)(cid:46) (cid:67)(cid:100)(cid:87)(cid:90)(cid:97)(cid:21)(cid:69)(cid:103)(cid:94)(cid:111)(cid:90)(cid:33)(cid:21)(cid:38)(cid:46)(cid:42)(cid:37) NameReactions Jie Jack Li Name Reactions A Collection of Detailed Reaction Mechanisms Third Expanded Edition 123 JieJackLi,Ph.D. PfizerGlobalResearchandDevelopment ChemistryDepartment 2800PlymouthRoad AnnArbor,MI48105 USA e-mail:jack.li@pfizer.com 3rd.expandeded. ISBN-103-540-30030-9 SpringerBerlinHeidelbergNewYork ISBN-13978-3-540-30030-4 SpringerBerlinHeidelbergNewYork e-ISBN3-540-30031-7 ISBN-103-540-40203-9 2nded.SpringerBerlinHeidelbergNewYork LibraryofCongressControlNumber:2006925628 This work is subject to copyright. All rights reserved, whether the whole or part of the materialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations, recitation,broadcasting,reproductiononmicrofilmorinanyotherway,andstorageindata banks.Duplicationofthispublicationorpartsthereofispermittedonlyundertheprovisions oftheGermanCopyrightLawofSeptember9,1965,initscurrentversion,andpermission forusemustalwaysbeobtainedfromSpringer.Violationsareliableforprosecutionunder theGermanCopyrightLaw. SpringerisapartofSpringerScience+BusinessMedia springer.com ©Springer-VerlagBerlinHeidelberg2003,2006 PrintedinGermany Theuseofgeneraldescriptivenames,registerednames,trademarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Typesetting:BytheAuthor Production:LE-TEX,Jelonek,Schmidt&VöcklerGbR,Leipzig Coverdesign:KünkelLopka,Heidelberg Printedonacid-freepaper 2/3100YL – 5 4 3 2 1 0 Dedicated to Professor E. J. Corey Foreword I don't have my name on anything that I don't really do. –Heidi Klum Can the organic chemists associated with so-called “Named Reactions” make the same claim as supermodel Heidi Klum? Many scholars of chemistry do not hesita- te 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 do with either Arndt or Eistert, Pummerer did not discover the “Pummerer” rearrange- ment, 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 reacti- ons”? Absolutely not. The above examples are merely exceptions to the rule. In fact, the chemists associated with name reactions are typically the original disco- verers, 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 ca- taloging 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 reacti- ons 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 dis- coveries 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 che- mistry for their contributions to metathesis, a name reaction that has been also in- cluded since the first edition. Therefore, I intend to keep up with the new devel- opments 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 Fi- scher 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 na- vigate 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 in- valuable 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 Cali- fornia 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, Na- thaniel Sherden, Jennifer Stockdill, and Carolyn Woodroofe for proofreading the final draft of the manuscript. Their knowledge and time have tremendously en- hanced 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...................................................................................................1 Aldol condensation..................................................................................................3 Algar–Flynn–Oyamada reaction.............................................................................5 Allan–Robinson reaction.........................................................................................8 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 Corey(cid:16)Chaykovsky 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-(cid:83)-methane rearrangement..............................................................................204 Doebner quinoline synthesis...............................................................................206 Dötz reaction.......................................................................................................208 Dowd–Beckwith ring expansion.........................................................................210 Erlenmeyer(cid:16)Plöchl 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 Tamao(cid:16)Kumada 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

See more

The list of books you might like

Most books are stored in the elastic cloud where traffic is expensive. For this reason, we have a limit on daily download.