HOMOGENEOUS CATALYSIS FOR UNREACTIVE BOND ACTIVATION HOMOGENEOUS CATALYSIS FOR UNREACTIVE BOND ACTIVATION Editedby ZHANG-JIE SHI ProfessorofChemistry CollegeofChemistryandMolecularEngineering PekingUniversity Beijing,China CoverImage:iStockphoto©saicle CoverDesign:Wiley Copyright©2015byJohnWiley&Sons,Inc.Allrightsreserved. PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey. PublishedsimultaneouslyinCanada. 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QD505.H6482014 541′.395–dc23 2014008375 PrintedintheUnitedStatesofAmerica. 10987654321 CONTENTS PREFACE xi CONTRIBUTORS xv 1 CATALYSISINC–ClACTIVATION 1 Zhong-XiaWangandWang-JunGuo 1.1 Introduction / 3 1.2 ReductiveDechlorination / 3 1.2.1 H asReductant / 3 2 1.2.2 ROHorROMasReductant / 6 1.2.3 HydrosilanesasReductant / 8 1.2.4 FormicAcidorItsSaltsasReductant / 11 1.2.5 BoraneorSodiumBorohydrideasReductant / 12 1.2.6 GrignardReagentsasReductant / 13 1.2.7 HydrazineasReductant / 14 1.3 FormationofC–CBonds / 14 1.3.1 SuzukiReaction / 14 1.3.2 NegishiReaction / 47 1.3.3 KumadaReaction / 57 1.3.4 StilleReaction / 70 1.3.5 HiyamaReaction / 74 1.3.6 SonogashiraReaction / 81 v vi CONTENTS 1.3.7 DecarboxylativeCross-Coupling / 86 1.3.8 HeckReaction / 89 1.3.9 C–HFunctionalizationwithOrganicChlorides / 97 1.4 FormationofC–NBonds / 119 1.4.1 CopperCatalysts / 119 1.4.2 PalladiumCatalysts / 124 1.4.3 NickelCatalysts / 141 1.4.4 IronandCobaltCatalysts / 143 1.5 FormationofC–OBonds / 143 1.5.1 CopperCatalysts / 143 1.5.2 PalladiumCatalysts / 145 1.6 FormationofC–SBonds / 148 1.6.1 CopperCatalysts / 149 1.6.2 PalladiumCatalysts / 149 1.7 FormationofC–BBonds / 151 1.7.1 PalladiumCatalysts / 151 1.7.2 NickelCatalysts / 152 1.8 ConclusionandOutlook / 154 References / 155 2 HOMOGENEOUSTRANSITION-METAL-CATALYZED C–FACTIVATION 203 Shang-DongYang 2.1 Background / 203 2.2 Transition-Metal-MediatedCross-CouplingReactions byC–FBondActivation / 205 2.2.1 Nickel-MediatedC–FBondActivation / 206 2.2.2 Palladium-MediatedC–FBondActivation / 219 2.2.3 Platinum-MediatedC–FBondActivation / 225 2.2.4 Cobalt-andRhodium-MediatedC–FBondActivation / 227 2.2.5 Other-Metals-MediatedC–FBondActivation / 231 2.3 Transition-Metal-CatalyzedSubstitutionbyC–FBond Activation / 234 2.4 Transition-Metal-PromotedDehydrofluorinationbyC–FBond Activation / 241 2.5 TheApplicationsofC–FActivationinOrganicSynthesis / 250 2.6 SummaryandOutlook / 257 References / 259 CONTENTS vii 3 HOMOGENEOUSTRANSITION-METALCATALYZED C–NACTIVATION 269 Xiao-BingWan 3.1 Background / 269 3.2 Palladium-CatalyzedC–NActivation / 270 3.3 Ruthenium-CatalyzedC–NActivation / 285 3.4 Nickel-CatalyzedC–NActivation / 289 3.5 Copper-CatalyzedC–NActivation / 292 3.6 Iron-CatalyzedC–NActivation / 296 3.7 Other-Transition–Metal-CatalyzedC–NActivation / 302 3.8 ComputationallyandExperimentallyMechanisticStudies / 313 3.9 SummaryandOutlook / 315 References / 315 4 CATALYTICCARBON–SULFURBONDACTIVATION ANDTRANSFORMATIONS 317 ZhengkunYu 4.1 Background / 317 4.2 C–SBondActivationbyTransitionMetalCompounds / 318 4.3 CatalyticC–SCleavageinThioesters / 321 4.4 CatalyticC–SCleavageinDithioacetals / 325 4.5 DiverseCatalyticC–SCleavage / 331 4.6 SummaryandOutlook / 337 References / 337 5 HOMOGENEOUSTRANSITION-METAL-CATALYZEDC–O BONDACTIVATION 347 Da-GangYu,ShuangLuo,FeiZhao,andZhang-JieShi 5.1 Introduction / 348 5.2 Palladium-CatalyzedC–OBondActivation / 354 5.2.1 Kumada–Tamao–CorriuCoupling / 354 5.2.2 NegishiCoupling(IncludingZinc,Aluminum, andManganeseReagents) / 356 5.2.3 StilleCoupling / 357 5.2.4 Suzuki–MiyauraCoupling / 359 5.2.5 HiyamaCoupling / 363 5.2.6 HeckReaction / 365 5.2.7 SonogashiraReaction / 367 viii CONTENTS 5.2.8 Cross-CouplingwithOtherC–HBondsandCarboxylic Acids / 369 5.2.9 CarbonylationReaction / 373 5.2.10Buchwald–HartwigAmination / 374 5.2.11OtherC–XBondFormationReactions / 379 5.3 Nickel–CatalyzedC–OBondActivation / 382 5.3.1 Kumada–Tamao–CorriuReaction / 382 5.3.2 NegishiCoupling(IncludingZinc,Aluminum,Manganese, Copper,andIndiumReagents) / 391 5.3.3 Suzuki–MiyauraCoupling / 392 5.3.4 HeckReaction / 403 5.3.5 Buchwald–HartwigAmination / 403 5.3.6 Borylation / 405 5.3.7 DirectArylation / 406 5.3.8 Reduction / 407 5.3.9 OtherReactions / 409 5.4 Other-Transition-Metal-CatalyzedC–OBondActivation / 409 5.4.1 Fe-CatalyzedC–OBondActivation / 409 5.4.2 Co-CatalyzedC–OBondActivation / 414 5.4.3 Cu-CatalyzedC–OBondActivation / 417 5.4.4 Rh-CatalyzedC–OBondActivation / 419 5.4.5 Ru-CatalyzedC–OBondActivation / 422 5.5 SummaryandOutlook / 426 References / 427 6 HOMOGENEOUSTRANSITION-METAL-CATALYZED C–HBONDFUNCTIONALIZATION 441 Bi-JieLiandZhang-JieShi 6.1 Overview / 442 6.2 MechanismofC–HCleavage / 444 6.2.1 OxidativeAddition / 444 6.2.2 ElectrophilicSubstitution / 448 6.2.3 SigmaBondMetathesis / 449 6.2.4 1,2-Addition / 450 6.2.5 MetalloradicalActivation / 452 6.3 DirectedC–HOxidation / 453 6.3.1 DirectedC–HOxygenation / 454 6.3.2 DirectedC–HAmination / 455