Handbook of Metathesis: Catalyst Development

1184 Pages·2003·27.15 MB·English

RobertH.Grubbs(Ed.)
HandbookofMetathesis
Catalyst Development
Handbook of Metathesis
Volume 1 – Catalyst Development
Volume 2 – Applications in Organic
Synthesis
Volume 3 – Applications in Polymer
Synthesis
Robert H. Grubbs (Ed.)
Handbook of Metathesis
Catalyst Development
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v
Contents
Volume1
Preface xxi
References xxv
ListofContributors xxvii
1.1 Introduction 1
RobertH.Grubbs
References 3
1.2 TheRoleofthe‘‘TebbeComplex’’inOlefinMetathesis 4
RobertH.Grubbs
References 6
1.3 TheDiscoveryandDevelopmentofHighOxidationStateMoandWImido
AlkylideneComplexesforAlkeneMetathesis 8
RichardR.Schrock
1.3.1 Introduction 8
1.3.2 TantalumAlkylideneComplexes 9
1.3.3 EarlyTungstenAlkylideneComplexes 13
1.3.4 DevelopmentofImidoAlkylideneComplexes 15
1.3.5 RheniumAlkylideneComplexes 20
1.3.6 DetailsofReactionsofImidoAlkylideneComplexesandTheoretical
Calculations 21
1.3.7 CatalystandReactionVariations 24
1.3.8 ConcludingRemarks 28
Acknowledgments 28
References 29
vi Contents
1.4 FromIll-DefinedtoWell-DefinedWAlkylideneComplexes 33
ChristopheCope´ret,Fre´de´ricLefebvre,andJean-MarieBasset
1.4.1 Introduction 33
1.4.2 OxoalkylideneWComplexes 33
1.4.3 Alkoxy-AlkylideneWComplexes:Kress-OsbornSystem 35
1.4.4 Aryloxy-AlkylideneWComplexes:Leconte-BassetSystem 37
1.4.5 AmidoalkylideneWComplexes 38
1.4.6 Imido-AlkylideneWComplexes:Schrock’sSystem 42
1.4.7 SummaryandOutlooks 44
References 45
1.5 FischerMetalCarbenesandOlefinMetathesis 47
ThomasJ.Katz
1.5.1 FischerMetalCarbenesandOlefinMetathesis 47
1.5.2 TheRoleofFischerMetalCarbenesinMetathesis 47
1.5.3 InductionofOlefinMetathesesbyFischerMetalCarbenes 49
1.5.3.1 Propertiesof2 49
1.5.3.2 OlefinMetathesesInitiatedbyMetalCarbene1 49
1.5.3.3 MechanisticImplications 51
1.5.3.4 MetathesesInitiatedbyMetalCarbene2 52
1.5.4 InitiationofAcetylenePolymerizationbyFischerMetalCarbenes 53
1.5.4.1 Introduction 53
1.5.4.2 ExamplesofAcetylenePolymerizationsInitiatedbyFischerMetal
Carbenes 54
1.5.5 ActuationofOlefinMetathesisbyAcetylenes 55
1.5.5.1 MetathesesofCyclicandAcyclicAlkenesActuatedbyAnAcetylene 55
1.5.5.2 ReactionofEnynesWithFischerMetalCarbenes 55
1.5.5.3 RearrangementofEnynestoDienes 56
References 57
1.6 TheDiscoveryandDevelopmentofWell-Defined,Ruthenium-BasedOlefin
MetathesisCatalysts 61
SonBinhT.NguyenandTinaM.Trnka
1.6.1 TheDiscoveryofWell-DefinedRutheniumOlefinMetathesisCatalysts:
APersonalAccountbySonBinhNguyen 61
1.6.1.1 (PPh ) Cl Ru CH CH CPh ,theFirstWell-Defined,Metathesis-Active
3 2 2 b a b 2
RutheniumAlkylideneComplex 62
1.6.1.2 (PCy ) Cl Ru CH CH CPh ,AWell-DefinedRutheniumAlkylidene
3 2 2 b a b 2
CatalystfortheMetathesisofAcyclicOlefins 63
1.6.1.3 InitialApplicationsofOlefinMetathesisChemistryCatalyzedby
(PCy3)2Cl2RubCHaCHbCPh2 64
1.6.2 MoreAccessibleRutheniumAlkylideneSources 65
1.6.3 2nd-GenerationGrubbsCatalysts 68
1.6.3.1 N-HeterocyclicCarbene(NHC)Ligands 70
Contents vii
1.6.4 Multi-ComponentRuthenium-BasedOlefinMetathesisCatalystSystems
andHomogeneousCatalystPrecursors 73
1.6.5 Solid-SupportedRuthenium-BasedOlefinMetathesisCatalysts 74
1.6.6 Conclusions 80
References 81
1.7 SynthesisofRutheniumCarbeneComplexes 86
WarrenR.Roper
1.7.1 Introduction 86
1.7.2 TheFirstRutheniumCarbeneComplexes 86
1.7.3 RutheniumMethyleneComplexes 88
1.7.4 RutheniumDihalocarbeneComplexes 92
Acknowledgments 93
References 93
1.8 SynthesisofRhodiumandRutheniumCarbeneComplexeswitha16-Electron
Count 95
HelmutWernerandJustinWolf
1.8.1 Introduction 95
1.8.2 Rhodium(I)CarbenesfromDiazoalkanes 95
1.8.3 Ruthenium(II)CarbenesandVinylidenesfromTerminalAlkynes 98
1.8.4 Conclusions 108
Acknowledgements 109
References 109
1.9 MechanismofRuthenium-CatalyzedOlefinMetathesisReactions 112
MelanieS.SanfordandJenniferA.Love
1.9.1 Introduction 112
1.9.2 First-GenerationBis-PhosphineCatalystSystems 112
1.9.2.1 GeneralMechanisticConsiderations 112
1.9.2.2 SubstituentEffectsinRuthenium-CatalyzedOlefinMetathesis 116
1.9.2.3 ThermalDecompositionofRutheniumCatalysts 118
1.9.2.4 DecompositioninthePresenceofFunctionalGroups 120
1.9.2.5 MechanisticConsiderationsinOtherFirst-GenerationRuthenium
MetathesisCatalysts 120
1.9.3 Second-GenerationRutheniumOlefinMetathesisCatalysts 123
1.9.3.1 GeneralMechanisticConsiderations 124
1.9.3.2 SubstituentEffectsinRuthenium-CatalyzedOlefinMetathesis 125
1.9.3.3 ThermalDecompositionofRutheniumCatalysts 127
1.9.3.4 DecompositioninthePresenceofFunctionalGroups 127
1.9.3.5 OtherSecond-GenerationRutheniumCatalysts 128
1.9.4 Conclusions 129
References 130
viii Contents
1.10 IntrinsicReactivityofRutheniumCarbenes 132
ChristianAdlhartandPeterChen
1.10.1 Introduction 132
1.10.2 ElectrosprayIonizationMassSpectrometry(ESIMS)ofTransitionMetal
Complexes 135
1.10.2.1 ElectrosprayIonization 135
1.10.2.2 TandemMassSpectrometry 136
1.10.2.3 ReactionConditionsintheCollisionCelloftheTandemESIMS 137
1.10.3 GeneralReactivityofRutheniumCarbeneComplexesintheGas
Phase 139
1.10.3.1 DissociativeMechanism 139
1.10.3.2 EvidenceforROMPandRCM 141
1.10.3.3 SystematicVariationofaCommonStructuralMotif–StericEffectsand
HalogenEffects 143
1.10.3.4 Conclusions 146
1.10.4 ThreeKeyFactorsthatDeterminetheActivityofMetathesis
Catalysts 147
1.10.4.1 Solution-PhasePre-Equilibria:Activation 147
1.10.4.2 Pre-EquilibriaDuringtheTurnover:Backbiting 148
1.10.4.3 CatalystCommitment:PotentialSurface 155
1.10.5 Conclusions 167
CompoundNumbers 167
References 169
1.11 TheDiscoveryandDevelopmentofHighOxidationStateAlkylidyne
ComplexesforAlkyneMetathesis 173
RichardR.Schrock
1.11.1 Introduction 173
1.11.2 AlkylidyneComplexesofTantalum 174
1.11.3 AlkylidyneComplexesofTungsten 174
1.11.4 FormationofTrialkoxyAlkylidyneComplexesfromW (OR)
2 6
Species 178
1.11.5 AlkylidyneComplexesofMolybdenum 180
1.11.6 ReactionsthatLimitMetathesisActivity 181
1.11.7 AlkylidyneComplexesofRhenium 185
1.11.8 ConclusionsandComments 186
Acknowledgments 187
References 187
1.12 Well-DefinedMetallocarbenesandMetallocarbynesSupportedonOxide
SupportsPreparedviaSurfaceOrganometallicChemistry:ASourceofHighly
ActiveAlkane,Alkene,andAlkyneMetathesisCatalysts 190
ChristopheCope´ret,Fre´de´ricLefebvre,andJean-MarieBasset
1.12.1 Introduction 190
1.12.2 PreparationandCharacterizationofWell-DefinedMetallocarbenesand
MetallocarbynesviaSurfaceOrganometallicChemistry 191
Contents ix
1.12.2.1 StrategyandToolsinSurfaceOrganometallicChemistry 191
1.12.2.2 ApplicationtothePreparationofWell-DefinedMetallocarbeneand
MetallocarbyneSupportedonOxides 192
1.12.3 ReactivityinAlkeneandAlkyneMetathesis 195
1.12.3.1 Group5and6MetallocarbenesandMetallocarbynesSupportedon
Oxides 195
1.12.3.2 Group7MetallocarbenesandMetallocarbynesSupportedon
Oxides 197
1.12.4 ReactivityinAlkaneMetathesis 200
1.12.5 SummaryandOutlook 201
Acknowledgments 202
References 202
Index 205
Volume2
ListofContributors xxi
2.1 OlefinMetathesisandRelatedReactionsinOrganicSynthesis:Introductionto
Metal-CarbonDoubleBondsinOrganicSynthesis 1
RobertH.Grubbs
References 4
2.2 GeneralRing-ClosingMetathesis 5
So-YeopHanandSukbokChang
2.2.1 Introduction 5
2.2.2 SynthesisofCarbocyles 7
2.2.2.1 Carbocyclization 7
2.2.2.2 Medium-SizedCarbocycles 16
2.2.2.3 SpiroCarbocycles 22
2.2.3 SynthesisofBridgedBicycloalkenes 24
2.2.4 SynthesisofHeterocyclesContainingSi,P,S,orB 29
2.2.4.1 Si-Heterocycles 29
2.2.4.2 P-Heterocycles 32
2.2.4.3 S-Heterocycles 35
2.2.4.4 B-Heterocycles 37
2.2.5 SynthesisofCyclicEthers 38
2.2.5.1 Mono-andBicyclicEthers 38
2.2.5.2 PolycyclicEthers 43
2.2.6 ApplicationstoN-HeterocyclesandPeptideChemistry 46
2.2.6.1 N-Heterocycles 46
2.2.6.2 SmallandMedium-SizedLactams 52
2.2.6.3 CyclicAminoAcids,Peptides,andPeptidomimetics 54
2.2.7 SynthesisofMacrocycles 65
2.2.7.1 Macrocycles 66
x Contents
2.2.7.2 Macrolactones 68
2.2.7.3 Macrolactams 73
2.2.8 SynthesisofCyclicConjugatedDienes 74
2.2.9 AlkyneMetathesis 77
2.2.10 EnyneMetathesis 80
2.2.10.1 GeneralEnyneMetathesis 80
2.2.10.2 DienyneMetathesis 83
2.2.11 Multi-DirectionalRCM 86
2.2.12 TandemProcesses 88
2.2.12.1 TandemROM/RCM 88
2.2.12.2 OtherTandemRCM 92
2.2.13 AsymmetricRCM 94
2.2.14 SynthesisofComplexMolecules 96
2.2.14.1 Template-DirectedRCM 96
2.2.14.2 RCMinSupramolecularChemistry 96
2.2.14.3 SyntheticApplications 109
References 119
2.3 CatalyticAsymmetricOlefinMetathesis 128
AmirH.Hoveyda
2.3.1 Introduction 128
2.3.2 TheCatalystConstruct 129
2.3.3 Mo-CatalyzedKineticResolutionWithHexafluoro-MoCatalysts 129
2.3.4 ChiralMo-DiolateComplexesforKineticResolutionandAsymmetric
Synthesis 130
2.3.4.1 ChiralBiphen-MoCatalysts 130
2.3.4.2 CatalyticKineticResolutionThroughMo-CatalyzedARCM 130
2.3.4.3 CatalystModularityandOptimizationofMo-CatalyzedARCMEfficiency
andSelectivity 131
2.3.4.4 CatalyticAsymmetricSynthesisThroughMo-CatalyzedARCM 133
2.3.4.5 CatalyticAsymmetricSynthesisThroughTandemMo-Catalyzed
AROM/RCM 137
2.3.4.6 CatalyticAsymmetricSynthesisThroughTandemMo-Catalyzed
AROM/CM 142
2.3.4.7 TowardsUser-FriendlyandPracticalChiralMo-BasedCatalystsfor
OlefinMetathesis 143
2.3.5 ChiralRu-BasedOlefinMetathesisCatalysts 145
2.3.6 ConclusionsandOutlook 147
Acknowledgments 148
References 148
2.4 TandemRing-ClosingMetathesis 151
StefanRandlandSiegfriedBlechert
2.4.1 Introduction 151
2.4.2 TandemMetathesisInvolvingDoubleBondsOnly 152
2.4.2.1 RRMofAlkenyl-SubstitutedCycloolefins 152
2.4.2.2 RRMofbisAlkenyl-SubstitutedCycloolefins 160