Edited by A. Stephen K. Hashmi and F. Dean Toste Modern Gold Catalyzed Synthesis Further Reading Mohr,F.(ed.) Ertl,G.,Knözinger,H.,Schüth,F., GoldChemistry Weitkamp,J.(eds.) HighlightsandFutureDirections HandbookofHeterogeneous 2009 Catalysis 8Volumes ISBN:978-3-527-32086-8 2008 Laguna,A.(ed.) ISBN:978-3-527-31241-2 ModernSupramolecular GoldChemistry Ding,K.,Uozumi,Y.(eds.) Gold-MetalInteractionsandApplications HandbookofAsymmetric 2008 HeterogeneousCatalysis 2008 ISBN:978-3-527-32029-5 ISBN:978-3-527-31913-8 Dupont,J.,Pfeffer,M.(eds.) Palladacycles Synthesis,Characterization andApplications 2008 ISBN:978-3-527-31781-3 Edited by A. Stephen K. Hashmi and F. Dean Toste Modern Gold Catalyzed Synthesis TheEditors AllbookspublishedbyWiley-VCHarecarefully produced.Nevertheless,authors,editors,andpub- Prof.Dr.A.StephenK.Hashmi lisherdonotwarranttheinformationcontainedin Organisch-ChemischesInstitut thesebooks,includingthisbook,tobefreeoferrors. UniversitätHeidelberg Readersareadvisedtokeepinmindthatstatements, ImNeuenheimerFeld270 data,illustrations,proceduraldetailsorotheritems 69120Heidelberg mayinadvertentlybeinaccurate. LibraryofCongressCardNo.: appliedfor Prof.F.DeanToste DepartmentofChemistry BritishLibraryCataloguing-in-PublicationData UniversityofCalifornia Acataloguerecordforthisbookisavailablefromthe Berkeley,CA94720-1460 BritishLibrary. USA Bibliographicinformationpublishedby theDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhispublica- tionintheDeutscheNationalbibliografie;detailed bibliographicdataareavailableontheInternetat http://dnb.d-nb.de. #2012Wiley-VCHVerlag&Co.KGaA, Boschstr.12,69469Weinheim,Germany Allrightsreserved(includingthoseoftranslation intootherlanguages).Nopartofthisbookmaybe reproducedinanyform–byphotoprinting,micro- film,oranyothermeans–nortransmittedortrans- latedintoamachinelanguagewithoutwritten permissionfromthepublishers.Registerednames, trademarks,etc.usedinthisbook,evenwhennot specificallymarkedassuch,arenottobeconsidered unprotectedbylaw. PrintISBN: 978-3-527-31952-7 ePDFISBN: 978-3-527-64689-0 ePubISBN: 978-3-527-64688-3 mobiISBN: 978-3-527-64687-6 oBookISBN: 978-3-527-64686-9 CoverDesign Formgeber,Eppelheim Typesetting ThomsonDigital,Noida,India PrintingandBinding betz-druckGmbH, Darmstadt,Germany V Contents List of Contributors XIII 1 HydrochlorinationofAcetyleneCatalyzedbyGold 1 MarcoConteandGrahamJ.Hutchings 1.1 Introduction 1 1.2 ReactionsofAlkynesUsingGoldChlorideasCatalyst 2 1.3 TheCorrelationofE88withtheActivityofGoldforthe HydrochlorinationofAcetylene 4 1.3.1 TheInitialCorrelation 4 1.3.2 ConceptualDevelopmentsoftheE8Correlation 5 1.3.3 FurtherStudyoftheCorrelationofE8withtheActivity ofPlatinumGroupMetals 8 1.3.4 TheE8CorrelationAppliedtoHomogeneousand NonhomogeneousGoldNanoalloys 9 1.4 CentralRoleofAu3þandRegenerationofAu/CCatalysts 12 1.5 ReactionMechanismofAlkynesOverAu/CCatalysts 14 1.5.1 EffectoftheIndividualComponentsoftheReactantstoAu/C 14 1.5.2 ReactionofHigherAlkynesOverAu/C 16 1.5.3 Hydrochlorinationof1-hexyne,phenylacetylene,and2-hexyne OverAu/CCatalyst 17 1.5.4 ComputationalStudiesoftheReactionofAcetyleneOverAu/C 21 1.6 ChemicalOriginoftheE8CorrelationandGeneralRemarks 22 1.7 CommercialProcessesandEconomicAspectsof VinylChlorideMonomerManufacture 24 References 25 2 Gold-CatalyzedReductionReactions 27 AvelinoCormaandPedroSerna 2.1 Introduction 27 2.2 HydrogenationofMultipleC¼CBonds.RoleoftheGold OxidationState 28 2.2.1 Introduction 28 VI Contents 2.2.2 FirstSolidGoldCatalysts:fromExtendedAuSurfacestoHighly DispersedNanoparticles 28 2.2.3 RecentAdvancesinSupportedGoldChemistry:fromHighly DispersedNanoparticlestoIndividualSupportedAuAtoms 31 2.2.4 Summary 34 2.3 Hydrogenationofa,b-UnsaturatedAldehydes 34 2.3.1 Introduction 34 2.3.2 ChemistryofGoldNanoparticles:FirstStudiesandHypotheses 36 2.3.3 StrongMetal–SupportInteractions:EffectofElectronicTransfers andDecorationontheGoldNanoparticles 37 2.3.4 EffectofMorphologicalFactors:SizeandShape 38 2.3.5 Summary 39 2.4 HydrogenationofSubstitutedNitroaromaticCompounds 41 2.4.1 Introduction 41 2.4.2 GoldCatalystsfortheProductionofSubstitutedNitroCompounds 42 2.4.3 Hydrogenationof–NO GroupsonGoldCatalysts: 2 ReactionPathway 43 2.4.4 ChemoselectivityofGoldCatalystsfortheHydrogenation ofNO groups 47 2 2.4.5 ActivityofGoldCatalystsfortheHydrogenationofNO 2 groups 49 2.4.6 Summary 51 References 51 3 Gold-CatalyzedBenzannulations:Asao–YamamotoBenzopyrylium Pathway 55 NaokiAsaoandYoshinoriYamamoto 3.1 Introduction 55 3.2 AcetylenicCompoundsas2pSystems 56 3.3 Enolsas2pSystems 60 3.4 EnolEthersas2pSystems 62 3.5 Benzynesas2pSystems 63 3.6 SynthesisofPhthalazineDerivatives 64 3.7 ApplicationtotheSynthesisofAngucyclinoneAntibiotics andOtherApplicationsinTotalSynthesis 65 3.8 Copper-CatalyzedBenzannulations 67 3.9 Conclusion 68 References 69 4 Gold-CatalyzedReactionsofPropargylEsters,PropargylAlcohols, andRelatedCompounds 75 PabloMauleonandF.DeanToste 4.1 IntroductionandExtentofThisChapter 75 4.2 PropargylEsters 76 Contents VII 4.2.1 GeneralMechanisticConsiderations 76 4.2.1.1 [2,3]-and[3,3]-Rearrangements 77 4.2.1.2 Reversibility 78 4.2.1.3 Ionization 80 4.2.1.4 Double[2,3]-Rearrangements 83 4.2.2 ReactionsInitiatedby[2,3]-Rearrangements 85 4.2.2.1 TheRautenstrauchRearrangement 86 4.2.2.2 AlkeneCyclopropanations 87 4.2.2.3 EnantioselectiveTransformationsAfter[2,3]-Rearrangements 92 4.2.2.4 NucleophilicAttackonGoldCarbenoidsGenerated After[2,3]-Rearrangements 94 4.2.3 ReactionsInitiatedby[3,3]-Rearrangements 96 4.2.3.1 NucleophilicDoubleBonds 97 4.2.3.2 TripleBonds 99 4.2.3.3 AromaticGroups 100 4.2.3.4 AlkylGroups 100 4.2.3.5 Heteroatoms 102 4.2.3.6 ElectrophilicTrappingofVinyl–GoldIntermediates 103 4.2.3.7 OtherProcesses 104 4.3 PropargylEthers 107 4.3.1 PropargylVinylEthers 107 4.3.2 PropargylAlkylEthers 110 4.3.3 OtherEtherSubstitutionPatterns 113 4.4 PropargylAlcohols 115 4.4.1 AlkyneHydration 115 4.4.2 Meyer–SchusterRearrangements 115 4.4.3 NucleophilicSubstitutionatthePropargylic Position 117 4.4.4 RingExpansions 117 4.4.5 OtherReactionsInvolvingPropargylAlcohols 119 4.5 PropargylAmines 121 4.6 PropargylCarbonates,Amides,andCarbamates 124 4.7 OtherPropargylSubstitutionPatterns 127 4.8 Conclusion 129 References 130 5 IntramolecularHydroarylationofAlkynes 135 PauladeMendozaandAntonioM.Echavarren 5.1 Introduction 135 5.2 IntramolecularReactionsofAreneswithAlkynes 137 5.3 IntramolecularReactionsofElectron-RichHeteroarenes withAlkynes 142 5.4 ConclusionandOutlook 148 References 148 VIII Contents 6 Gold–AlkyneComplexes 153 MariaAgostinaCinellu 6.1 Introduction 153 6.2 DescriptionoftheM–p-BondInteractioninAlkeneandAlkyne Complexes 154 6.3 Gold(0)Complexes 155 6.4 Gold(I)Complexes 155 6.4.1 NeutralDerivatives 155 6.4.2 CationicDerivatives 158 6.4.3 p-ComplexationofGold(I)atMetal–AlkynylUnitsM–C(cid:2)C–R 164 6.5 Gold(III)complexes 167 6.6 TheoreticalStudies 167 References 171 7 Gold–AlkeneComplexes 175 MariaAgostinaCinellu 7.1 Introduction 175 7.2 Gold(0)Derivatives 176 7.3 Gold(I)Complexes 176 7.3.1 NeutralDerivatives 176 7.3.1.1 14-ElectronSpecies 176 7.3.1.2 16-ElectronSpecies 178 7.3.2 CationicDerivatives 181 7.3.2.1 14-ElectronSpecies 181 7.3.2.2 16-ElectronSpecies 186 7.4 Gold(III)Complexes 191 7.5 TheoreticalStudies 192 References 196 8 HydrationandHydroalkoxylationofCCMultipleBonds 201 J.HenriqueTeles 8.1 HistoricalPerspective 201 8.1.1 AdditionofWatertoAlkynes 201 8.1.2 AdditionofAlcoholstoAlkynes 202 8.2 GoldCatalysts 202 8.2.1 FirstReportsofGoldCatalysts 203 8.2.2 TheDiscoveryofAu(I)Catalysts 204 8.2.2.1 CatalystPrecursors 206 8.2.2.2 TheImportanceofChemicalEquilibria 208 8.3 HydrationandHydroalkoxylationofCCTripleBonds(Alkynes) 209 8.3.1 EffectofAlcoholStructure 209 8.3.2 AdditionofWatertoAlkynes 211 8.3.3 AdditionofAlcoholstoSimpleAlkynes 215 8.3.4 ReactionsInvolvingPropargylicAlcohols 217 8.3.5 AdditionstoHomopropargylicAlcoholsandOtherAlkynols 220 Contents IX 8.3.6 ReactionsInvolvingPropargylicEthers 224 8.4 HydrationandHydroalkoxylationofCCDoubleBonds (AllenesandAlkenes) 226 8.4.1 AdditionofAlcoholstoAllenes 226 8.4.2 CyclizationofAllenylandPropargylKetones 227 8.4.3 AdditionofAlcoholstoAlkenes 230 References 234 9 Gold-CatalyzedAldolandRelatedReactions 237 ChristophHubbertandA.StephenK.Hashmi 9.1 TheGold-CatalyzedAldolReaction 237 9.1.1 SyntheticScope 239 9.1.1.1 ReactionsofAldehydeswithMethylIsocyanoacetate 239 9.1.1.2 ReactionsofAldehydeswitha-SubstitutedIsonitriles 241 9.1.1.3 ReactionsofAldehydeswithAlkylIsocyanoacetates 242 9.1.1.4 ReactionsofAldehydeswithAlkylIsocyanoacetamides 243 9.1.1.5 ReactionsofAldehydeswitha-IsocyanoWeinrebAmide 244 9.1.1.6 ReactionsofAldehydeswithIsocyanoPhosphonates 245 9.1.1.7 ReactionsofAldehydeswitha-KetoEsters 246 9.1.2 StructureoftheLigand 247 9.1.2.1 InternalCooperativityofChirality 248 9.1.2.2 ConformationofthePendantSideChain 251 9.1.3 MechanisticAspects 253 9.1.3.1 TheFirstTransition-StateModel 253 9.1.3.2 StructureoftheFerrocenyl–Gold(I)Complex 253 9.1.3.3 MechanisticAspects 253 9.2 RelatedReactions 257 9.2.1 SynthesisofDihydroimidazole 257 9.2.2 MannichReactions 258 9.2.3 MichaelReactions 259 References 260 10 Gold-CatalyzedOxidationReactions:OxidationofAlkenes 263 YuanhongLiu 10.1 Introduction 263 10.2 EpoxidationReactions 263 10.3 AziridinationReactions 268 10.4 OxidativeCleavageofC¼CDoubleBonds 269 10.5 OxygenTransfertoCarbenoids 270 References 271 11 Gold-CatalyzedOxygen-AtomTransfertoAlkynes 273 MariaCamilaBlancoJaimesandA.StephenK.Hashmi 11.1 Introduction 273 11.2 Oxygen-AtomTransferfromNOGroups 273 X Contents 11.2.1 Nitrones 274 11.2.2 NitroCompounds 276 11.2.3 N-Oxides 277 11.3 Oxygen-AtomTransferfromSulfoxides 280 11.4 Oxygen-AtomTransferfromEpoxides 282 11.5 Gold-CatalyzedOxidativeCoupling 283 11.5.1 Introduction 283 11.5.2 FunctionalizationofC(sp2)–HBonds 284 11.5.3 Gold-CatalyzedNucleophilicAddition–OxidativeCoupling Reactions 287 References 295 12 Gold-CatalyzedAdditionstoAlkenes:N-Nucleophiles 297 ZigangLi,DavidA.Capretto,andChuanHe References 302 13 Gold-CatalyzedAdditionstoAlkenes:O-Nucleophiles 303 ZigangLi,DavidA.Capretto,andChuanHe References 307 14 OxidationofAlcoholsandCarbohydrates 309 CristinaDellaPina,ErmelindaFalletta,andMicheleRossi 14.1 Introduction 309 14.2 SelectiveOxidationofAlcohols 310 14.2.1 CatalystPreparation 311 14.2.2 OxidationofDiols 312 14.2.3 OxidationofOtherPolyols 315 14.2.3.1 Glycerol 315 14.2.3.2 Sorbitol 317 14.2.3.3 OtherAlcohols 317 14.2.3.4 AminoAlcohols 318 14.3 SelectiveOxidationofCarbohydrates 320 14.3.1 OxidationofGlucosetoSodiumGluconate 321 14.3.1.1 KineticsandModeling 323 14.3.2 SynthesisofFreeGluconicAcid 325 14.4 FutureApplications 326 14.5 Conclusion 327 References 328 15 ApplicationsofGold-CatalyzedReactionstoNatural ProductSynthesis 331 MatthiasRudolph 15.1 Introduction 331 15.2 AdditionofHeteroatomNucleophilestoAlkynes 332 15.2.1 HydrationofAlkynes:PterosinBandC 332 15.2.2 Tandem Reaction Including Hydration of Alkynes, Elimination, and ConjugateAddition:(þ)-Andrachcinidine 332