Table Of ContentEditedby
A(cid:1)rp(cid:1)adMoln(cid:1)ar
Palladium-Catalyzed
CouplingReactions
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Edited by A(cid:1)rp(cid:1)ad Moln(cid:1)ar
Palladium-Catalyzed Coupling Reactions
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V
Contents
Foreword XIII
Preface XV
ListofContributors XVII
1 Palladium-CatalyzedCross-CouplingReactions–AGeneral
Introduction 1
KlausK€ohler,KatharinaWussow,andAndreasSebastianWirth
1.1 Introduction 1
1.1.1 HistoricalReflection 1
1.1.2 Characteristics,RecentDevelopments,andProgress 2
1.1.3 LiteratureReviewsandOrganizationoftheChapter 3
1.2 Carbon–CarbonCross-CouplingReactionsCatalyzed
byPalladium 4
1.2.1 ClassificationandOverview 4
1.2.2 CommonMechanisticFeaturesofCross-CouplingReactionsand
ReactivityoftheSubstrates 8
1.2.2.1 ChoiceoftheCarbonElectrophile 9
1.2.2.2 ChoiceoftheCarbonNucleophile–WhatMakestheDifference? 9
1.3 TheCatalysts 10
1.3.1 TheParticularFeaturesofPalladium 10
1.3.2 ClassesofPalladiumCatalystsAppliedtoCross-CouplingReactions 12
1.3.2.1 LigandsandPalladiumComplexes–HomogeneousSystems 13
1.3.2.2 ImmobilizedorSupportedPalladiumComplexesand
Particles–HeterogeneousSystems 17
1.3.2.3 PalladiumColloidsand(Nonsupported)Nanoparticles 17
1.3.2.4 ActivityofHeterogeneousCatalysts 18
1.4 MechanisticAspects 18
1.4.1 GeneralMechanismofC(cid:1)(cid:1)CCross-CouplingandHeckReactionswith
HomogeneousCatalystPrecursors 18
1.4.2 ModelsforHeckandSuzukiReactionswithSupported
PdPrecursors 19
1.4.3 RecentResultsontheReactionMechanismandtheNatureofthe
ActivePdSpecies 21
j
VI Contents
1.4.3.1 ObservationofIntermediatesinHomogeneousCatalysisby
ElectrochemicalMethods 21
1.4.3.2 TheQuestionofPdLeaching 22
1.4.3.3 SelectivityPattern 23
1.4.3.4 InSituObservationbySpectroscopicMethods 24
1.4.3.5 ImmobilizedPdPincerComplexes 24
1.4.3.6 PalladiumBulkMaterials(PdFoil,Wire,Sponge)asCatalyst 24
1.5 FutureChallenges 25
Abbreviations 27
References 27
2 High-TurnoverHeterogeneousPalladiumCatalystsinCoupling
Reactions:theCaseofPdLoadedonDealuminatedYZeolites 31
KazuOkumura
2.1 Introduction 31
2.2 VariousMethodologiestoAffordHighTurnoverNumbersOver
SupportedPdCatalysts 32
2.3 StructureandCharacteristicsofUltrastableYZeolites 33
2.4 Suzuki–MiyauraReactionsCatalyzedbyPd/USY 35
2.4.1 CatalyticPerformanceofPd/USY 35
2.4.2 PdLeachingfromPd/USY 40
2.4.3 SelectivityintheHomocouplingReactions 41
2.4.4 CharacterizationoftheActivePdSpeciesbyX-RayAbsorption
Spectroscopy 41
2.4.5 ASuggestedMechanismfortheFormationofActivePdSpeciesin
Suzuki–MiyauraCouplingReactions 46
2.5 CatalyticPerformanceofPd/USYinMizoroki–Heck
Reactions 48
2.5.1 EffectofH BubblingontheCatalyticReactionsofPd/USY 48
2
2.5.2 CatalyticReactionsUsingChlorobenzeneDerivatives 51
2.5.3 CharacterizationofthePdSpeciesbyX-RayAbsorption
Spectroscopy 53
2.6 ConclusionandPerspective 54
Abbreviations 55
References 55
3 Palladium-CatalyzedCouplingReactionswithMagneticallySeparable
Nanocatalysts 57
KifahS.M.SalihandWernerR.Thiel
3.1 Introduction 57
3.2 GeneralConsiderationsConcerningMagneticParticlesasCatalyst
Supports 57
3.3 PalladiumNanoparticlesonMagneticSupports 59
3.4 MolecularPalladiumComplexesonMagneticSupports 68
3.5 Outlook 75
j
Contents VII
Abbreviations 76
References 77
4 TheUseofOrderedPorousSolidsasSupportMaterialsin
Palladium-CatalyzedCross-CouplingReactions 79
A(cid:2)rp(cid:2)adMoln(cid:2)ar
4.1 Introduction 79
4.2 CatalystSynthesisandCharacterization 80
4.3 Carbon–CarbonCouplings 85
4.3.1 Zeolites 85
4.3.2 MesoporousOrderedSilicaMaterials 94
4.3.2.1 CouplingReactionsCatalyzedbySupportedPalladiumParticles 94
4.3.2.2 ReactionsMediatedbyImmobilizedPalladiumSpecies 103
4.3.3 PeriodicMesoporousOrganosilicas 116
4.3.4 CatalystsBasedonNonsiliceousSolids 121
4.3.4.1 Metal–OrganicFrameworks 121
4.3.4.2 CovalentOrganicFrameworks 123
4.3.4.3 OtherSupportMaterials 124
4.4 MiscellaneousCouplingReactions 127
4.5 TheQuestionofSolution-PhaseCatalysis 130
4.6 SummaryandFutureProspects 131
Abbreviations 133
References 134
5 CouplingReactionsInducedbyPolymer-SupportedCatalysts 141
BabakKarimi,SedighehAbedi,andAsgharZamani
5.1 Introduction 141
5.2 Polysaccharides 143
5.2.1 Starch 143
5.2.2 Chitosan 145
5.2.3 OtherPolysaccharides 148
5.3 Poly(ethyleneglycol) 150
5.3.1 NonfunctionalizedPoly(ethyleneglycol) 150
5.3.2 FunctionalizedPoly(ethyleneglycol) 152
5.4 Polystyrene 155
5.4.1 NonfunctionalizedPolystyrene 155
5.4.2 FunctionalizedPolystyrene 156
5.4.2.1 Polystyrene-SupportedLigandsContainingNitrogen 156
5.4.2.2 Polystyrene-SupportedTriphenylphosphane 161
5.5 Poly(norbornene) 165
5.6 Polyacrylamide 167
5.7 Polyaniline 170
5.8 Poly(N-vinyl-2-pyrrolidone) 171
5.9 Polypyrrole 173
5.10 Poly(4-vinylpyridine) 174
j
VIII Contents
5.11 IonicPolymers 175
5.11.1 OrganicPolymersContainingN-HeterocyclicCarbenesorIonic
Liquids 176
5.11.2 PolymersContainingOtherIonicLigands 183
5.12 OrganometallicPolymers 184
5.13 FunctionalizedPorousOrganicPolymers 188
5.14 MiscellaneousPolymers 189
5.15 SummaryandOutlook 192
Abbreviations 193
References 195
6 CouplingReactionsinIonicLiquids 201
MichaelT.Keßler,JacksonD.Scholten,FrankGalbrecht,andMartinH.G.
Prechtl
6.1 Introduction 201
6.2 MetalComplexes 204
6.2.1 Mizoroki–HeckReaction 205
6.2.2 SonogashiraCoupling 209
6.2.3 Suzuki–MiyauraCoupling 212
6.2.4 NegishiCoupling 213
6.2.5 Trost–TsujiCoupling 214
6.3 MetalSaltsandMetalonSolidSupport 214
6.3.1 Mizoroki–HeckReaction 215
6.3.2 Suzuki–MiyauraReaction 218
6.3.3 StilleReaction 219
6.4 MetalNanoparticles 220
6.4.1 TheMizoroki–HeckReactionwithPdNPsinILs 222
6.4.2 Suzuki–MiyauraReaction 224
6.4.3 StilleReaction 226
6.4.4 Buchwald–HartwigReaction 227
6.4.5 SonogashiraReaction 228
6.4.6 UllmannReaction 228
6.5 SummaryandOutlook 229
Abbreviations 230
References 231
7 Cross-CouplingReactionsinAqueousMedia 235
KevinH.Shaughnessy
7.1 Introduction 235
7.2 Cross-CouplingofOrganicHalidestoFormC(cid:1)(cid:1)CBondsin
AqueousMedia 236
7.2.1 SuzukiCoupling 236
7.2.1.1 Aqueous-PhaseSuzukiCouplingUsingHydrophilicLigand-Supported
Catalysts 237
7.2.1.2 OnWaterSuzukiCouplingswithHydrophobicCatalystSystems 248
j
Contents IX
7.2.1.3 Surfactant-PromotedAqueous-PhaseSuzukiCouplings 249
7.2.1.4 PalladiumCatalystsSupportedonHeterogeneousSupports 251
7.2.1.5 PalladiumNanoparticleCatalysts 253
7.2.2 StilleCoupling 256
7.2.3 HiyamaCoupling 257
7.2.4 NegishiCoupling 259
7.2.5 SonogashiraCoupling 260
7.2.6 ArylationofOtherCarbanionNucleophiles 268
7.2.7 HeckCoupling 270
7.3 Carbon–HeteroatomCouplingReactions 274
7.3.1 AminationofArylHalides 274
7.3.2 OtherCarbon–HeteroatomCouplingReactions 276
7.4 C(cid:1)(cid:1)HActivationinAqueousMedia 277
7.5 ConclusionandFutureProspects 279
Abbreviations 279
References 281
8 Microwave-AssistedSynthesisinC(cid:1)(cid:1)CandCarbon–Heteroatom
CouplingReactions 287
Ke-HuWangandJin-XianWang
8.1 Introduction 287
8.2 C(cid:1)(cid:1)CBondFormation 288
8.2.1 HeckCouplingReactions 288
8.2.2 SuzukiReactions 295
8.2.3 NegishiCouplings 308
8.2.4 CouplingofTerminalAlkyneswithArylHalides 310
8.2.5 CouplingReactionsofOrganostannaneswithOrganicHalides 312
8.2.6 CouplingsofOrganosilaneswithArylHalides 313
8.2.7 CyanationofArylHalides 315
8.2.8 CarbonylationReactions 316
8.2.9 DecarboxylativeCouplings 318
8.2.10 OtherC(cid:1)(cid:1)CBondFormations 319
8.3 C(cid:1)(cid:1)XBondFormation 321
8.3.1 C(cid:1)(cid:1)NBondFormation 321
8.3.2 C(cid:1)(cid:1)PBondFormation 325
8.4 Conclusions 327
Abbreviations 327
References 328
9 CatalystRecyclinginPalladium-CatalyzedCarbon–CarbonCoupling
Reactions 333
A(cid:2)rp(cid:2)adMoln(cid:2)ar
9.1 Introduction 333
9.2 GeneralIssuesofCatalystRecycling 333
9.3 CatalystSystemsProvidingHigh,ConsistentYieldsinRecycling 337
j
X Contents
9.3.1 TheUseofCatalystswithPdParticles 337
9.3.2 RecyclingofPalladiumComplexes 346
9.3.2.1 ComplexesAnchoredtoInorganicSupports 346
9.3.2.2 ComplexesImmobilizedonPolymers 355
9.3.2.3 Self-SupportedPolymericComplexes 361
9.3.3 StudiesPerformedUnderHomogeneousConditions 362
9.4 CatalystsAffordingtheHighestCumulativeTONValuesinRecycling
Studies 370
9.4.1 CatalystswithSupportedParticles 370
9.4.2 ImmobilizedComplexes 373
9.5 SummaryEvaluation 375
9.6 FutureOutlook 381
Abbreviations 382
References 383
10 NatureoftheTrueCatalyticSpeciesinCarbon–CarbonCoupling
ReactionswithHeterogeneousPalladiumPrecatalysts 387
LinHuangandPuiKwanWong
10.1 Introduction 387
10.2 HeckReactions 389
10.2.1 SupportedPdParticles 389
10.2.2 ImmobilizedPdComplexes 394
10.3 SuzukiReactions 396
10.3.1 SupportedPdParticles 396
10.3.2 ImmobilizedPdComplexes 398
10.4 SonogashiraReactions 402
10.4.1 SupportedPdParticles 402
10.4.2 ImmobilizedPdComplexes 403
10.5 ConcludingRemarks 404
Abbreviations 406
References 406
11 CouplingReactionsinContinuous-FlowSystems 409
WilliamR.ReynoldsandChristopherG.Frost
11.1 Introduction 409
11.2 CouplingReactionsinFlow 410
11.2.1 Suzuki–MiyauraCoupling 410
11.2.2 Mizoroki–HeckCoupling 413
11.2.3 SonogashiraCoupling 415
11.2.4 MurahashiCoupling 416
11.2.5 HiyamaCoupling 418
11.2.6 CarbonylativeCouplings 418
11.2.7 Buchwald–HartwigAmination 420
11.3 PalladiumCatalystsforFlowSystems 422
11.3.1 HeterogeneousSupportedCatalysts 422
