Modern AlleneChemistry现代艾伦化学 英文版.pdf

Modern Allene ChemistryEdited byNorbert Krause and A.Stephen K.HashmiModern Allene Chemistry.Edited by N.Krause and A.S.K.HashmiCopyright?2004 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN:3-527-30671-4Further Titles of InterestR.Gleiter,H.Hopf(Eds.)Modern Cyclophane Chemistry2004,ISBN 3-527-30713-3R.Mahrwald(Ed.)Modern Aldol ReactionsTwo Volumes2004,ISBN 3-527-30714-1T.Takeda(Ed.)Modern Carbonyl OlefinationMethods and Applications2004,ISBN 3-527-30634-XD.Astruc(Ed.)Modern Arene ChemistryConcepts,Synthesis,and Applications2002,ISBN 3-527-30489-4Modern Allene ChemistryVolume 1Edited byNorbert Krause and A.Stephen K.HashmiEditorsProfessor Dr.Norbert KrauseUniversity of DortmundOrganic Chemistry IIOtto-Hahn-Strasse 644227DortmundGermanyProfessor Dr.A.Stephen K.HashmiUniversity of StuttgartDepartment of Organic ChemistryPfaffenwaldring 5570569StuttgartGermany&All books published by Wiley-VCH are carefully pro-duced.Nevertheless,authors,editors,and publisherdo not warrant the information contained in thesebooks,including this book,to be free of errors.Readers are advised to keep in mind that statements,data,illustrations,procedural details or other itemsmay inadvertently be inaccurate.Library of Congress Card No.:applied forBritish Library Cataloguing-in-Publication DataA catalogue record for this book is available from theBritish Library.Bibliographic information published byDie Deutsche BibliothekDie Deutsche Bibliothek lists this publication in theDeutsche Nationalbibliografie;detailed bibliographicdata is available in the Internet at?2004 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimAll rights reserved(including those of translationinto other languages).No part of this book may bereproduced in any form nor transmitted or trans-lated into machine language without written permis-sion from the publishers.Registered names,trade-marks,etc.used in this book,even when notspecifically marked as such,are not to be consideredunprotected by law.Printed in the Federal Republic of GermanyPrinted on acid-free and chlorine-free paperCover designSCHULZ Grafikdesign,FugAnheimCompositionKBhn&Weyh,Satz und Medien,FreiburgPrintingbetz-druck GmbH,DarmstadtBookbindingJ.SchFffer GmbH,GrBnstadtISBN3-527-30671-4VVolume 1ISynthesis of Allenes11Synthesis of Allenes by Isomerization Reactions3A.Stephen K.Hashmi1.1Introduction31.2Prototropic Rearrangements and Related Reactions of Alkynes61.2.1Hydrogen Atoms or Alkyl Groups as Substituents61.2.2Alkenyl or Aryl Groups as Substituents91.2.3Alkinyl Groups as Substituents121.2.4Carbonyl Groups as Substituents131.2.5Halogens as Substituents171.2.6Oxygen as the Substituent191.2.7Nitrogen as the Substituent211.2.8Sulfur as the Substituent231.2.9Silyl and Stannyl Substituents251.2.10Phosphorus as the Substituent261.2.11Allenes from Prototropic Isomerizations of Alkynes as ReactiveIntermediates271.3Sigmatropic Rearrangements271.3.12,3-Sigmatropic Rearrangements271.3.23,3-Sigmatropic Rearrangements291.4Rearrangements of Other Systems with at Least Two p-Bonds331.5Retro-Ene Reactions331.6Electrocyclic Ring Openings341.7Intramolecular Conjugate Additions341.8Complex Reactions and Rearrangements351.9Conclusion36ContentsModern Allene Chemistry.Edited by N.Krause and A.S.K.HashmiCopyright 8 2004 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN:3-527-30671-4Contents2Metal-Mediated Synthesis of Allenes51Anja Hoffmann-R?der and Norbert Krause2.1Introduction2.2Copper-Mediated Synthesis of Allenes522.2.1Substitution Reactions522.2.2Addition Reactions612.3Lithium-,Magnesium-and Zinc-Mediated Synthesis of Allenes702.4Aluminum-and Indium-Mediated Synthesis of Allenes752.5Titanium-and Samarium-Mediated Synthesis of Allenes792.6Conclusion873Transition Metal-Catalyzed Synthesis of Allenes93Masamichi Ogasawara and Tamio Hayashi3.1Introduction933.2Formation of Allenes by Substitution Reactions933.2.1SN2 Substitution of Propargyl Compounds933.2.2SN2 Substitution of 2-Halo-1,3-Butadienes and RelatedCompounds1123.2.3SN2 Substitution of Pent-2-en-4-ynyl Acetates1173.2.4SE2 Substitution of PropargylMetal Species1183.3Formation of Allenes by Addition Reactions1213.3.11,4-Addition to Conjugated Enynes and Related Reactions1213.3.21,6-Conjugate Addition to Enynylcarbonyl Compounds1283.4Formation of Allenes by Elimination Reactions1293.5Other Miscellaneous Methods of Preparing Allenes1313.6Formation of 1,2,3-Butatrienes1333.7Conclusion1364Enantioselective Synthesis of Allenes141Hiroaki Ohno,Yasuo Nagaoka,and Kiyoshi Tomioka4.1Introduction1414.2Chirality Transfer from Propargylic Compounds1414.2.1Organocopper-Mediated Alkylation of Propargyl AlcoholDerivatives1414.2.2Copper-Mediated Halogenation of Propargyl Alcohol Derivatives1484.2.3Rearrangement of Propargyl Alcohol Derivatives1524.2.4Palladium(0)-Catalyzed Reactions of Propargyl Alcohol Derivatives1554.2.5SN2 Reduction of Propargyl Alcohol Derivatives1584.2.6Ring-Opening Reactions of Propargyl Epoxides and RelatedCompounds1604.2.7Chiral Propargyl or AllenylMetal Reagents163VIContents4.3Elimination Reactions of Chiral Allylic Compounds1654.3.1Chirality Transfer from Allylic Position1654.3.2Elimination Reactions of Allylic Compounds Having a Chiral LeavingGroup1684.4Synthesis of Allenes Using Chiral Reagents1694.4.1Asymmetric DeprotonationProtonation1694.4.2Asymmetric HornerWadsworthEmmons and Related Reactions1714.5Direct Asymmetric Synthesis of Allenes Using an External ChiralCatalyst1714.6Synthesis of Allenes Using Internal Chiral Auxiliaries1754.7Kinetic Resolution1754.8Conclusion177IISpecial Classes of Allenes1835Allenic Hydrocarbons Preparation and Use in Organic Synthesis185Henning Hopf5.1Introduction1855.2Allenic Hydrocarbons from Simple Building Blocks1865.3Preparation of Allenic Hydrocarbons1885.3.1General Methods1885.3.2Alkylallenes1905.3.3Vinylallenes1945.3.4Ethynylallenes1975.3.5Conjugated Bisallenes1995.3.6Cyclopropylallenes2025.3.7Arylallenes2045.3.8Allenes Carrying Other Unsaturated Substituents2095.3.9Semicyclic Allenic Hydrocarbons2175.4Allenic Hydrocarbons as Reaction Intermediates2185.5Why Allenic Hydrocarbons Are of Interest in Preparative OrganicChemistry2226Cyclic Allenes Up to Seven-Membered Rings243Manfred Christl6.1Introduction2436.2Three-,Four-and Five-Membered Rings2456.3Six-Membered Rings2486.3.1Unsubstituted 1,2-Cyclohexadiene2486.3.2Substituted 1,2-Cyclohexadienes2606.3.3Bridged and Annulated 1,2-Cyclohexadienes2666.3.41,2,4-Cyclohexatriene,3d2-1H-Naphthalene and Their Derivatives2726.3.5Heterocyclic Derivatives of 1,2,4-Cycloheptatriene(162)and3d2-1H-Naphthalene(221)289VIIContents6.3.6Heterocyclic Derivatives of 1,2-Cyclohexadiene(6)2996.4Seven-Membered Rings3246.4.11,2-Cycloheptadiene and Its Simple Derivatives3256.4.21,2,4,6-Cycloheptatetraene and Its Simple Derivatives3326.4.3Annulated and Bridged Derivatives of 1,2-Cycloheptadiene3496.4.4Heterocyclic Derivatives of 1,2-Cycloheptadiene3507Acceptor-Substituted Allenes359Klaus Banert and Jens Lehmann7.1Introduction3597.2Synthesis of Acceptor-Substituted Allenes3607.2.1Methods with Building Up of the Carbon Skeleton of the Allene3607.2.2Prototropic Isomerization of Propargyl Compounds3617.2.32,3-Sigmatropic Rearrangement of Propargyl Compounds3647.2.4Other Rearrangement Reactions3677.2.5Nucleophilic Substitution of Propargyl Compounds3697.2.6Palladium-Catalyzed Carbonylation of Propargyl Compounds3717.2.71,4-Addition to Enynes3737.2.8Elimination and Cleavage Reactions3737.2.9Introduction of the Acceptor Substituent into the Allene3757.2.10Synthesis from Other Acceptor-Substituted Allenes3787.3Reactions of Acceptor-Substituted Allenes3797.3.1Nucleophilic Addition3797.3.2Nucleophilic Addition Including Ring Closure3867.3.3Electrophilic Addition3907.3.4Ring Closure to Form Carbocycles3927.3.5Ring Closure to Produce Heterocycles3957.3.6DielsAlder Reactions4017.3.7Other Cycloaddition Reactions4067.3.8Sigmatropic Rearrangement Reactions4117.3.9Other Rearrangement Reactions4147.3.10Miscellaneous Reactions4157.4Conclusion4168Donor-Substituted Allenes425Reinhold Zimmer and Hans-Ulrich Reissig8.1Introduction4258.2O-Substituted Allenes4278.2.1Synthesis of O-Substituted Allenes4278.2.2Deprotonation of Alkoxyallenes and Reaction with Electrophiles Ring-Closing Reactions4318.2.3Cycloadditions and Cyclizations4498.2.4Formation of Acetals and Subsequent Metathesis Reactions4588.2.5Miscellaneous Reactions of O-Substituted Allenes462VIIIContents8.3N-Substituted Allenes4678.3.1Synthesis of N-Substituted Allenes4678.3.2Reactions of N-Substituted Allenes4718.4S-and Se-Substituted Allenes4758.4.1Synthesis of S-Substituted Allenes4758.4.2Reactions of S-Substituted Allenes4788.4.3Synthesis and Reactions of Se-Substituted Allenes4848.5Conclusion4859Synthesis and Reactions of Allenylmetal Compounds493James A.Marshall,Benjamin W.Gung,and Melissa L.Grachan9.1Introduction4939.1.1Preparation4939.1.2Reaction Characteristics4949.2Allenyllithium Reagents4979.2.1Structure4979.2.2Regioselectivity of Silylation5009.3Allenylcopper Reagents5089.4Allenylmagnesium Halides5099.5Allenylboron Reagents5109.6Allenyltitanium Reagents5179.7Allenylsilanes5279.8Allenylstannanes5439.8.1Allenyltin Halide Reagents5439.8.2Trialkylallenyltin Reagents5469.8.3Reactions of Chiral Allenyltin Reagents5489.8.4Synthesis and Reactions of Chiral Allenyltin Halides5519.8.5Chiral Catalysis5549.8.6Oxygenated Allenyltin Halides5559.8.7Intramolecular Additions5569.9Allenylpalladium Reagents5589.9.1Synthesis5589.9.2Cross-Coupling Reactions5599.9.3Decarboxylation5619.9.4Carbonylation5629.9.5Cyclizations and Cascade Reactions5639.10Allenylzinc Reagents5659.10.1Racemic Allenylzinc Reagents5669.10.2Enantioenriched Chiral Allenylzinc Reagents5689.11Allenylindium Reagents5749.11.1MetalHalogen Exchange5769.11.2Chiral Lewis Acids5849.12Miscellaneous Allenylmetal Reagents585IXContentsVolume 2IIIReactions of Allenes59310Ionic Additions to Allenes595Shengming Ma11Fundamentals and Application of Free Radical Addition to Allenes701Jens Hartung and Thomas Kopf12Cycloadditions of Allenes727Masahiro Murakami and Takanori Matsuda13Cyclizations of Allenes817Marcus A.Tius14Transition Metal-Catalyzed Cross-Couplings of Allenes847Reinhold Zimmer and Hans-Ulrich Reissig15Transition Metal-Catalyzed Cycloisomerizations of Allenes877A.Stephen K.Hashmi16Transition Metal-Catalyzed Addition/Cycloaddition of Allenes925Tadakatsu Mandai17Oxidation of Allenes973Attila Horv.th and Jan-E.B0ckvallIVApplications99518Allenic Natural Products and Pharmaceuticals997Norbert Krause and Anja Hoffmann-R?der19Allenes in Natural Product Synthesis1041Kay M.Brummond and Hongfeng Chen20EnyneAllenes1091Kung K.WangSubject Index1127XXIChemists have always been fascinated by the cumulated diene system of alleneswith its extraordinary properties,such as the axial chirality of the elongated tetra-hedron and a higher reactivity than non-cumulated C-C double bonds.Over the past20years allenes have become increasingly popular among chemists,and even occu-pied fields where their use was previously difficult due to selectivity problems tran-sition metal-catalyzed reactions,for example.At the end of 2000,Stephen Hashmipublished a highlight on such new and selective transition metal-catalyzed reactionsof allenes.Subsequently,Henning Hopf turned our attention to the fact that fol-lowing a series of books on allenes(including such well known volumes as MllersHouben-Weyl issue on allenes,Patais issue on allenes,Brandsmas wonderful labo-ratory manual and Landors“Chemistry of Allenes”)the last monograph on thetopic,Schuster/Coppola“Allenes in Organic Synthesis”,appeared back in 1984 andnow,after 20years,it might be time for a new one.A closer survey revealed that in the period elapsed since 1984 an average of400publications on allenes have appeared each year,amounting to close to 8000 intotal.This made it obvious that one mortal author could not cover the whole fieldalone.As a consequence,Norbert Krause,both a renowned expert in allene chemis-try and experienced in editing books,was commissioned as an additional editor.Thecrucial part then was to identify those fields of allene chemistry displaying the newand significant developments since 1984.We decided to divide the project into fourparts,“Synthesis of Allenes”,“Special Classes of Allenes”,“Reactions of Allenes”,and“Applications”.Twenty chapters cover such new and exciting developments as metal-catalyzedsynthesis of allenes,strained cyclic allenes,the numerous applications of differentmetallated allenes in organic synthesis,as well as the many addition and rearrange-ment reactions of allenes and allene units in natural products like the remarkableenyne-allenes.For these chapters an international team of 16authors,all experts in their respec-tive fields of allene chemistry,was put together and did an extraordinary job in com-piling this two-volume handbook.We are very grateful for their effort,as well as forthe organizational skills of Dr.Bettina Bems and Dr.Gudrun Walter from Wiley-VCH.Special thanks go also to Kerstin Hammerschmidt-Assmann for editing theover 1600chemical drawings of this monograph.PrefaceModern Allene Chemistry.Edited by N.Krause and A.S.K.HashmiCopyright 2004 WILEY-VCH Verlag GmbH&Co.KGaA,WeinheimISBN:3-527-30671-4From the chapters of this book it is evident that the allene group is more versatilethan ever before and that the developments in new reactions are still proceeding at ahigh rate,such that we are not witnessing the decreasing slide after a peak of scien-tific interest,but rather a continuous development.We are confident that this book will be both a very useful source for scientiststeaching chemistry and an inspiration for all those involved in chemical research.Dortmund and Stuttgart,Norbert KrauseSeptember 2004A.Stephen K.HashmiPrefaceXIIModern Allene ChemistryVolume 2Edited byNorbert Krause and A.Stephen K.HashmiContentsVolume 2IIIReactions of Allenes59310Ionic Additions to Allenes595Shengming Ma10.1Unfunctionalized Allenes59510.1.1Electrophilic Additions59510.1.2Nucleophilic Additions60310.2Allenylsilanes60410.2.1Electrophilic Additions60410.31,2-Allenyl Sulfides60810.41,2-Allenyl Ethers60910.4.1Electrophilic Additions60910.4.2Nucleophilic Additions61310.51,2-Allenyl Halides61410.5.1Electrophilic Additions61410.5.2Nucleophilic Additions61510.6Phosphorus-Containing Allenes61910.6.1Electrophilic Addition61910.6.2Nucleophilic Addition62110.71,2-Allenyl Sulfoxides62610.7.1Electrophilic Additions62610.7.2Nucleophilic Additions62610.81,2-Allenyl Sulfones62910.8.1Electrophilic Additions62910.8.2Nucleophilic Additions63010.9Allenylamines63810.9.1Electrophilic Additions63810.9.2Nucleophilic Additions64710.102,3-Allenols65010.10.1Electrophilic Additions65010.10.2Nucleophilic Additions65410.111,2-Allenic Ketones65910.11.1Electrophilic Additions65910.11.2Nucleophilic Additions66110.122,3-Allenoic Acids and 2,3-Allenoates66710.12.1Electrophilic Additions66710.12.2Nucleophilic Additions66910.132,3-Allenamides68010.13.1Electrophilic Additions68010.13.2Nucleophilic Additi