N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis

569 Pages·2014·7.556 MB·English

by  Steven P. Nolan

Edited by Steven P. Nolan
N-Heterocyclic
Carbenes
Effective Tools for Organometallic Synthesis

Editedby
StevenP.Nolan
N-HeterocyclicCarbenes
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Edited by Steven P. Nolan
N-Heterocyclic Carbenes
Effective Tools for Organometallic Synthesis
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And to Catherine, Maëlys and Kaelia, for always being there.”

VII
Contents
ListofContributors XVII
Preface XXI
1 N-HeterocyclicCarbenes 1
DavidJ.NelsonandStevenP.Nolan
1.1 Introduction 1
1.2 StructureandPropertiesofNHCs 1
1.3 AbnormalCarbenes 5
1.4 WhyAreNHCsStable? 6
1.5 BondingofNHCstoMetalCenters 8
1.6 QuantifyingthePropertiesofNHCs 13
1.6.1 StericImpact 13
1.6.2 ElectronicProperties 14
1.7 N-HeterocyclicCarbenesintheContextofOtherStableCarbenes 16
1.8 SynthesisofNHCs 19
1.9 SaltsandAdductsofNHCs 20
1.10 Summary 22
References 22
2 TuningandQuantifyingStericandElectronicEffectsof
N-HeterocyclicCarbenes 25
LauraFalivene,AlbertPoater,andLuigiCavallo
2.1 Introduction 25
2.2 StericEffectsinNHCligands 26
2.3 ElectronicEffectsinNHCLigands 31
2.4 Conclusions 35
References 35
3 ChiralMonodendateN-HeterocyclicCarbeneLigandsinAsymmetric
Catalysis 39
LinglinWu,AlvaroSalvador,andRetoDorta
3.1 Introduction 39
VIII Contents
3.2 NHC–Ru 40
3.2.1 AsymmetricMetathesis 40
3.2.2 AsymmetricHydrogenation 44
3.2.3 AsymmetricHydrosilylation 47
3.3 NHC–Rh 48
3.3.1 AsymmetricCatalysisUsingBoronicAcidsas
Nucleophiles 48
3.3.2 AsymmetricHydrosilylation 50
3.3.3 AsymmetricHydroformylation 53
3.4 NHC–Ir 53
3.5 NHC–Ni 55
3.6 NHC–Pd 56
3.6.1 AsymmetricIntramolecularα-Arylationof
Amides 56
3.6.2 AsymmetricDiamination 62
3.6.3 OtherAsymmetricCatalysisUsingNHC–Pd 63
3.7 NHC–Cu 65
3.7.1 AsymmetricConjugateAddition 65
3.7.2 AsymmetricAllylicSubstitution 67
3.7.3 SilylConjugateAddition 69
3.7.4 Enantioselectiveβ-Boration 70
3.7.5 AsymmetricHydrosilylation 72
3.7.6 AsymmetricAdditiontoImines 73
3.8 NHC–Ag 75
3.9 NHC–Au 75
3.9.1 EnantioselectiveCycloisomerizations 76
3.9.2 EnantioselectiveHydrogenation 78
3.9.3 EnantioselectiveCycloaddition 79
3.10 Conclusion 79
References 80
4 (N-HeterocyclicCarbene)–PalladiumComplexes
inCatalysis 85
MarioHoyos,DanielGuest,andOscarNavarro
4.1 Introduction 85
4.2 Cross-CouplingReactions 85
4.2.1 Suzuki–MiyauraCoupling 85
4.2.2 Buchwald–HartwigAminations 88
4.2.3 NegishiReactions 89
4.2.4 HiyamaCoupling 89
4.2.5 KumadaCoupling 90
4.2.6 SonogashiraCoupling 90
4.2.7 HeckReaction 92
4.3 ChelatesandPincerLigands 93
4.4 AsymmetricCatalysis 97