Cleavage of Carbon-Carbon Single Bonds by Transition Metals

293 Pages·2015·21.416 MB·English

by  Masahiro Murakami, Naoto Chatani

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