Lewis Base Catalysis in Organic Synthesis, 3 Volume Set

1441 Pages·2016·97.396 MB·English

by  Edwin Vedejs, Scott E. Denmark

EdwinVedejs
ScottE.Denmark
Lewis Base Catalysis in Organic Synthesis

Edwin Vedejs and Scott E. Denmark
Lewis Base Catalysis in Organic Synthesis
Volume 1, 2 and 3
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V
Contents
Preface XXVII
Introduction:DefinitionsofCatalysis XXXIII
Volume1
1 FromCatalysistoLewisBaseCatalysiswithHighlightsfrom1806to1970 1
EdwinVedejs
1.1 Introduction 1
1.2 Catalysis 1
1.2.1 BerzeliusDefinesCatalysis 2
1.2.2 EarlyProposalsforIntermediatesinCatalyticReactions 2
1.3 ProgresswithCatalysisinOrganicChemistry 3
1.4 Ostwald’sRedefinitionofCatalysis 5
1.4.1 TheEvolutionofOstwald’sViewsandTheirSubsequentRefinement 5
1.4.2 Sabatierand“TemporaryCompounds”inHeterogeneousCatalysis 6
1.4.3 ACuriousTangent:TheRadiationHypothesisforCatalysis 6
1.5 TheFirstExampleofLewisBaseCatalysis 7
1.6 TheRoadtoMechanisticComprehension;MultistageCatalysisbyLewisBase 9
1.6.1 TheKnoevenagelCondensation 9
1.6.2 Lapworth’sBreakthrough;BenzoinRevisited 11
1.7 AnUnevenPathtoaUnifyingConcept 12
1.7.1 HalideCatalysis 12
1.7.2 AmbidentNucleophileIntermediatesinHalide-CatalyzedRearrangements 14
1.7.3 TheFirstRecognitionofLewisBaseCatalysis 14
1.8 AmineCatalysis 17
1.8.1 Amine-CatalyzedDecarboxylation 17
1.8.2 TheThiamineStory:AmineCatalysisIsSlowerThanN-HeterocyclicCarbeneCatalysis 18
1.8.3 AmineActivationofAnhydrides 20
1.8.3.1 EarlyExamplesofAnhydrideActivation 20
1.8.3.2 GoldandJefferson:TheFirstMechanisticStudy 20
1.8.4 ModelSystemsasProbesofEnzymeFunction 21
1.8.4.1 Bender’sSummaryof“Nucleophilic”Catalysis 21
1.8.4.2 AcetylPhosphateHydrolysis 23
VI Contents
1.8.5 MiscellaneousExamplesofLewisBaseCatalysis 24
1.8.5.1 Dakin–WestReaction 24
1.8.5.2 MiscellaneousCatalyticApplicationsofNeutralandAnionicLewisBases 25
1.9 Summary 26
Acknowledgement 27
References 27
SectionIPrinciples 31
2 Principles,Definitions,Terminology,andOrbitalAnalysisofLewis
Base–LewisAcidInteractionsLeadingtoCatalysis 33
ScottE.DenmarkandGregoryL.Beutner
2.1 Introduction 33
2.2 LewisDefinitionsofValenceandtheChemicalBond 34
2.2.1 The“RuleofTwo” 34
2.2.2 ElectronicTheoryofAcidsandBases 35
2.3 Extensions,Expansionsof,andObjectionstotheLewisDefinitions 35
2.4 InterpretationoftheLewisDefinitionsintheIdiomofMolecularOrbitalTheoryand
QuantumMechanics 38
2.4.1 TheMullikenDefinition 38
2.4.2 TheLewis–Mulliken–JensenDefinition 39
2.5 DefiningLewisBaseCatalysis 40
2.5.1 Why“LewisBaseCatalysis”andNot“NucleophilicCatalysis” 42
2.5.2 LewisBaseCatalysisorLigand-AcceleratedCatalysis? 42
2.5.3 ClassificationofInteractionsInvolvedinLewisBaseCatalysis 43
2.5.3.1 CatalysisbyNucleophilicAddition:n®π*Interactions 43
2.5.4 CatalysisbyPolarization:n®σ*andn®n*Interactions 44
2.6 TheoreticalAnalysisoftheGeometricalandElectronicConsequencesofLewis
Acid–LewisBaseInteractions 44
2.6.1 ValenceBondAnalysis 44
2.6.2 PerturbationMolecularOrbitalTheoryAnalysis 45
2.6.3 GutmannAnalysis 46
2.6.4 HypervalentBondingAnalysis 49
2.6.5 NaturalBondOrbital(NBO)Analysis 51
2.7 Summary 51
References 52
3 ThermodynamicTreatmentsofLewisBasicity 55
Jean-FrançoisGal
3.1 Introduction 55
3.2 BasicThermodynamicsfortheStudyofLewisAcid–BaseInteractions 56
3.3 ScalesofLewisAffinityandBasicity 58
3.3.1 ReferenceLewisAcids:ExperimentalConsiderations 58
3.3.2 Enthalpy(Affinity)versusGibbsEnergy(Basicity)asaMeasureofLewisAcid–Base
Interactions 61
3.4 LewisAcidityandLewisBasicity:ThermodynamicScales 62
Contents VII
3.4.1 SolventsandSimpleFunctionalities 62
3.4.2 MethylCationAffinities 68
3.4.3 LewisBasewithBindingSitesContainingHeavierPnictogenandChalcogenElements 72
3.5 QuantumChemicalTools 74
3.6 ConclusionandOverview 75
3.7 Summary 76
ListofAbbreviations 77
Acknowledgment 78
References 78
4 QuantitativeTreatmentsofNucleophilicityandCarbonLewisBasicity 85
SamiLakhdar
4.1 Introduction 85
4.2 Nucleophilicity 85
4.2.1 TheSwain–ScottandEdwardsApproaches 85
4.2.2 TheRitchieEquation 87
4.2.3 TheMayrEquation 89
4.3 LewisBasicity 91
4.4 Nucleofugality 93
4.5 SelectedApplications 95
4.5.1 PyridinesandDerivatives 95
4.5.2 TertiaryAmines 99
4.5.3 IsothioureaDerivatives 101
4.5.4 PhosphinesandPhosphites 102
4.5.5 N-HeterocyclicCarbenes 104
4.5.6 ChiralEnamines 107
4.6 Conclusion 113
4.7 Summary 113
ListofAbbreviations 113
Acknowledgments 114
References 114
SectionIIMechanismandLewisBaseCatalysis:NucleophilicityIsOnlyPartoftheStory 119
5 AnhydrideActivationby4-DialkylaminopyridinesandAnalogs(n®π*) 121
RamanTandonandHendrikZipse
5.1 HistoricalBackground 121
5.2 MechanisticConsiderations 121
5.3 CatalystStructureandVariation 124
5.4 TheInfluenceofReactionConditions 130
5.5 TheInfluenceofAcylDonors 132
5.6 TheInfluenceofSubstrateStructure 136
5.7 Summary 141
ListofAbbreviations 142
References 142
VIII Contents
6 MechanisticUnderstandingofProlineAnalogsandRelatedProtic
LewisBases(n®π*) 145
AlanArmstrongandPaulDingwall
6.1 ProlineCatalysis:Overview 145
6.1.1 TheLimitationsofProlineasaCatalyst 146
6.2 MechanismoftheProline-CatalyzedAldolReaction 147
6.2.1 TheHajos–Parrish–Eder–Sauer–Wiechert(HPESW)Reaction 148
6.2.2 TheHouk–ListModel 150
6.2.2.1 AGeneralCatalyticCycle 150
6.2.2.2 TheRoleofEnamineIntermediates 152
6.2.2.3 RationalizingtheOriginsofStereoselectivity 153
6.2.2.4 AdvancesinComputationalChemistry 156
6.2.3 AnAlternativetotheHouk–ListModel:TheSeebach–EschenmoserModel 158
6.2.4 WaterasanAdditive 159
6.2.4.1 EffectofOtherAdditives 161
6.3 MechanismoftheProline-Catalyzedα-Aminationandα-AminoxylationReactions 161
6.3.1 ProticAdditives 161
6.3.2 BasicAdditivesandProlinateSalts 166
6.4 TheProline-MediatedConjugateAdditionReaction 170
6.4.1 PeptidicProlineAnalog 174
6.5 ModifiedProlineDerivatives 175
6.5.1 ProlineTetrazole 176
6.5.2 TheHouk–ListModelandProlineAnalogs 179
6.5.2.1 Cyclopropane-FusedProline 179
6.5.2.2 β-ProlineAnalogs 180
6.5.2.3 ConstrainedBicycleProlineAnalogs 182
6.5.2.4 PyrrolidineRingConformationandNCHδ+∙∙∙Oδ Interactions 182
6.5.2.5 MannichReaction:DesignedAnti-SelectiveCatalyst 182
6.5.3 ProlineAnalogsandAdditives 183
6.5.3.1 α-MethylProlineandTriethylamineintheα-AlkylationReaction 183
6.5.3.2 (2S,5S)-Pyrrolidine-2,5-DicarboxylicAcidandTriethylamine 185
6.6 ConcludingRemarks 186
ListofAbbreviations 187
References 187
7 MechanisticOptionsfortheMorita–Baylis–HillmanReaction(n®π*) 191
MariliaS.Santos,JoséTiagoM.Correia,AnaPaulaL.Batista,ManoelT.RodriguesJr.,
AtaualpaA.C.Braga,MarcosN.Eberlin,andFernandoCoelho
7.1 TheMorita–Baylis–HillmanReaction:AnOverview 191
7.2 KineticStudiesAppliedtoaza-Morita–Baylis–HillmanReaction 195
7.2.1 EarlyStudiesofIsaacsandHill 195
7.2.2 BodeandKaye’sKineticInvestigations 197
7.2.3 McQuadeKineticInvestigations:ProposalofaMoreComplexMBHMechanismin
AproticSolvents 198
7.2.4 AggarwalKineticStudies:ProposalofanAutocatalyticMechanism 201
7.2.5 KineticStudiesRelatedtoaza-Morita-Baylis-HillmanReaction 203