Table Of Content

Editedby MasahiroMurakamiand NaotoChatani CleavageofCarbon-CarbonSingle BondsbyTransitionMetals RelatedTitles Grubbs,R.H.,Wenzel,A.G.,O’Leary,D.J., Bates,R.R. Khosravi,E.(eds.) OrganicSynthesisUsing HandbookofMetathesis TransitionMetals SecondEdition SecondEdition 2015 2012 PrintISBN:978-3-527-33424-7;alsoavailable PrintISBN:978-1-119-97894-7;alsoavailable inelectronicformats inelectronicformats Shi,Z.(ed.) Christmann,M.,Bräse,S.(eds.) HomogeneousCatalysisfor AsymmetricSynthesisII UnreactiveBondActivation MoreMethodsandApplications 2015 2012 PrintISBN:978-1-118-45223-3;alsoavailable PrintISBN:978-3-527-32921-2;alsoavailable inelectronicformats inelectronicformats Ananikov,V.P.(ed.) Andersson,P.G.(ed.) Understanding InnovativeCatalysisinOrganic OrganometallicReaction Synthesis MechanismsandCatalysis Oxidation,Hydrogenation,andC-XBond FormingReactions ComputationalandExperimentalTools 2012 2014 PrintISBN:978-3-527-33097-3;alsoavailable PrintISBN:978-3-527-33562-6;alsoavailable inelectronicformats inelectronicformats Li,C.,Liu,Y.(eds.) BridgingHeterogeneousand HomogeneousCatalysis Concepts,Strategies,andApplications 2014 PrintISBN:978-3-527-33583-1;alsoavailable inelectronicformats EditedbyMasahiroMurakamiandNaotoChatani Cleavage of Carbon-Carbon Single Bonds by Transition Metals TheEditors AllbookspublishedbyWiley-VCH arecarefullyproduced.Nevertheless, Prof.Dr.MasahiroMurakami authors,editors,andpublisherdonot KyotoUniversity warranttheinformationcontainedin DepartmentofSyntheticChemistryand thesebooks,includingthisbook,to BiologicalChemistry befreeoferrors.Readersareadvised Katsura tokeepinmindthatstatements,data, Kyoto615-8510 illustrations,proceduraldetailsorother Japan itemsmayinadvertentlybeinaccurate. LibraryofCongressCardNo.:appliedfor Prof.Dr.NaotoChatani OsakaUniversity BritishLibraryCataloguing-in-Publication DepartmentofAppliedChemistry Data Suita Acataloguerecordforthisbookis Osaka565-0871 availablefromtheBritishLibrary. Japan Bibliographicinformationpublishedbythe DeutscheNationalbibliothek TheDeutscheNationalbibliothek liststhispublicationintheDeutsche Nationalbibliografie;detailedbiblio- graphicdataareavailableontheInter- netat<http://dnb.d-nb.de>. ©2016Wiley-VCHVerlagGmbH&Co. KGaA,Boschstr.12,69469Weinheim, Germany Allrightsreserved(includingthoseof translationintootherlanguages).No partofthisbookmaybereproduced inanyform – byphotoprinting,micro- film,oranyothermeans – nortrans- mittedortranslatedintoamachine languagewithoutwrittenpermission fromthepublishers.Registerednames, trademarks,etc.usedinthisbook,even whennotspecificallymarkedassuch, arenottobeconsideredunprotectedby law. PrintISBN:978-3-527-33632-6 ePDFISBN:978-3-527-68010-8 ePubISBN:978-3-527-68011-5 MobiISBN:978-3-527-68012-2 oBookISBN:978-3-527-68009-2 CoverDesign Grafik-DesignSchulz, Fußgönheim,Germany Typesetting SPiGlobal,Chennai,India PrintingandBinding MarkonoPrint MediaPteLtd.,Singapore Printedonacid-freepaper V Contents Preface IX ListofContributors XI 1 FundamentalReactionstoCleaveCarbon–Carbon𝛔-Bondswith TransitionMetalComplexes 1 MasahiroMurakamiandNaokiIshida 1.1 Introduction 1 1.2 OxidativeAddition 1 1.2.1 OxidativeAdditionUtilizingRingStrain 3 1.2.2 Chelation-AssistedOxidativeAddition 5 1.2.3 OxidativeAdditionDrivenbyAromatization 6 1.2.4 OxidativeAdditionofKetones 7 1.2.5 OxidativeAdditionofNitriles 11 1.2.6 Others 13 1.3 β-CarbonElimination 14 1.3.1 β-CarbonEliminationofLateTransitionMetalAlkyls 15 1.3.2 β-CarbonEliminationfromEarlyTransitionMetalAlkyls 16 1.3.3 β-CarbonEliminationofLateTransitionMetalAlcoholates 17 1.4 Retroallylation 20 1.5 MigratoryDeinsertionofaCarbonylGroup 22 1.6 Decarboxylation 24 1.7 Retro-oxidativeCyclization 25 1.8 1,2-Migration 27 1.9 CleavageofC–CMultipleBonds 29 1.10 Summary 30 References 30 2 ReactionsofThree-MemberedRingCompounds 35 TakanoriMatsuda 2.1 Introduction 35 2.2 Cyclopropanes 35 2.3 Bicyclo[1.1.0]butanes 40 2.4 Bicyclo[2.1.0]pentanes 43 VI Contents 2.5 QuadricyclanesandRelatedCompounds 45 2.6 Spiropentanes 47 2.7 Cyclopropanols 48 2.8 Vinylcyclopropanes 51 2.9 Methylenecyclopropanes 59 2.10 Alkynylcyclopropanes 70 2.11 CyclopropylKetonesandImines 71 2.12 Cyclopropenes 73 2.13 Benzocyclopropenes 78 2.14 Cyclopropenones 80 2.15 Conclusion 82 References 83 3 ReactionsofFour-MemberedRingCompounds 89 TakanoriMatsuda 3.1 Introduction 89 3.2 CubaneDerivatives 89 3.3 Biphenylenes 90 3.4 VinylcyclobutaneandMethylenecyclobutaneDerivatives 93 3.5 CyclobutanolandCyclobutanoneDerivatives 95 3.5.1 ReactionsInvolvingβ-CarbonEliminationofTransitionMetal Cyclobutanolates 95 3.5.2 ReactionsInvolvingFormationofFive-Membered Metallacycles 108 3.6 CyclobutenonesandCyclobutenediones 112 3.7 Conclusion 115 References 115 4 ReactionsInvolvingEliminationofCO andKetones 119 2 TetsuyaSatohandMasahiroMiura 4.1 Introduction 119 4.2 ReactionsofBenzoicAcids 119 4.2.1 Arylation 119 4.2.2 Alkenylation 127 4.2.3 Annulation 130 4.2.4 MiscellaneousReactions 132 4.3 ReactionsofHeteroarenecarboxylicAcids 134 4.4 ReactionsofAcrylicAcids 139 4.5 ReactionsofPropiolicAcids 142 4.6 Reactionsofα-KetoCarboxylicAcids 144 4.7 ReactionsofAlkanoicAcids 148 4.8 ReactionsofTertiaryAlcohols 151 4.8.1 Arylation 151 4.8.2 Alkenylation,Annulation,andAlkylation 155 Contents VII 4.9 SummaryandConclusions 159 References 160 5 Retro-allylationandDeallylation 165 HidekiYorimitsu 5.1 Introduction 165 5.2 Retro-allylation 165 5.2.1 RutheniumCatalysis:ThePioneer 167 5.2.2 PalladiumCatalysis:Regio-andStereoselectiveAllylationofAryl Halides 168 5.2.2.1 AdvantageofPalladium-CatalyzedAllylationvia Retro-allylation 168 5.2.2.2 Palladium-CatalyzedRegio-andStereoselectiveAllylationvia Retro-allylation 170 5.2.2.3 VariantsofPalladium-CatalyzedRetro-allylation 176 5.2.3 NickelCatalysis 179 5.2.4 RhodiumCatalysis 181 5.2.5 CopperCatalysis 184 5.3 Deallylation 185 5.3.1 OxidativeAdditionofAllylicCompounds 185 5.3.2 Metalation–β-CarbonEliminationSequence 187 5.4 SummaryandConclusions 189 References 190 6 ReactionsviaCleavageofCarbon–CarbonBondsofKetonesand Nitriles 193 MamoruTobisu 6.1 Introduction 193 6.2 CatalyticReactionsofKetonesviaC–CBondCleavage 194 6.2.1 ReactionsofKetoneswithoutChelationAssistance 194 6.2.2 ReactionsofKetonesContainingaDirectingGroup 196 6.2.3 ReactionsofKetonesUsingaTemporaryDirectingGroup 200 6.2.4 C–CBondCleavageofKetonesviaPathwaysOtherthanOxidative Addition 202 6.2.4.1 C–CBondCleavageof1,3-DicarbonylCompounds 202 6.2.4.2 C–CBondCleavageofKetonesOtherthan1,3-Dicarbonyl Compounds 203 6.3 CatalyticReactionsofNitrilesviaC–CBondCleavage 205 6.3.1 C–CNBondCleavageviaOxidativeAddition 205 6.3.2 C–CNBondCleavageviaSilylmetalation/IsocyanideExtrusion Sequence 212 6.3.3 C–CNBondCleavageviaOtherMechanisms 215 6.4 SummaryandOutlook 216 References 217 VIII Contents 7 Miscellaneous 221 MasahiroMurakamiandNaokiIshida 7.1 Introduction 221 7.2 CleavageofC–CSingleBonds 221 7.3 CleavageofC=CDoubleBonds 235 7.4 CleavageofC–CBondsofAromatics 237 7.5 CleavageofC≡CTripleBonds 242 7.6 Summary 248 References 248 8 TotalSynthesesofNaturalProductsandBiologicallyActive CompoundsbyTransition-Metal-CatalyzedC–CCleavage 253 MasahiroMurakamiandNaokiIshida 8.1 Introduction 253 8.2 Synthesisof(±)-NanaomycinAthroughAlkyneInsertionintoa C–CBondofBenzocyclobutenedione 253 8.3 EnantioselectiveSynthesisof(−)-PseudolaricAcidBviaan Intramolecular[5+2]CycloadditionReactionofaVinylcyclopropane withanAlkyne 254 8.4 EnantioselectiveSynthesisof(−)-EsermetholeviaAsymmetric AlkeneInsertionintoaC–CBondofArylCyanides 256 8.5 EnantioselectiveSynthesisofBenzobicyclo[2.2.2]octenonesvia AsymmetricAlkeneInsertionintoaC–CBondof Cyclobutanones 257 8.6 SynthesisoftheProposedStructureofCycloinumakiolthrough Site-SelectiveInsertionofAlkenesintoaC–CBondof Benzocyclobutenones 259 8.7 EnantioselectiveSynthesisof(−)-(R)-Herbertenolthrough AsymmetricC–CCleavage 260 8.8 EnantioselectiveSynthesisof(+)-LaureneviaRing-Expansionof 1-Vinylcyclobutanol 261 8.9 Synthesisof(±)-CuparenonethroughSkeletalReorganizationof Spiropentanes 262 8.10 TotalSynthesisof(−)-CyanthiwiginFbyDecarboxylative AsymmetricAllylation 264 8.11 TotalSynthesesviaHydrogenolysisofCyclopropanes 265 8.12 TotalSynthesesviaDecarbonylation 266 8.13 SummaryandConclusions 269 References 270 Index 273