2010年诺贝尔化学奖获得者及其主要贡献 7页

2010年诺贝尔化学奖获得者及其主要贡献美国化学家RichardF.Heck日本科学家根岸荣一和铃木章贡献①HeckReactionThepalladium-catalyzedC-Ccouplingbetweenarylhalidesorvinylhalidesandactivatedalkenesinthepresenceofabaseisreferredasthe"HeckReaction".RecentdevelopmentsinthecatalystsandreactionconditionshaveresultedinamuchbroaderrangeofdonorsandacceptorsbeingamenabletotheHeckReaction.OneofthebenefitsoftheHeckReactionisitsoutstandingtransselectivity.机理 最近文献AnEfficientandGeneralMethodfortheHeckandBuchwald-HartwigCouplingReactionsofArylChloridesD.-H.Lee,A.Taher,S.Hossain,M.-J.Jin,Org.Lett.,2011,13,5540-5543.Palladium-CatalyzedHeckReactionofArylChloridesunderMildConditionsPromotedby OrganicIonicBasesH.-J.Xu,Y.-Q.Zhao,X.-F.Zhou,J.Org.Chem.,2011,76,8036-8041.EfficientAqueous-PhaseHeckReactionCatalyzedbyaRobustHydrophilicPyridine-BridgedBisbenzimidazolylidene-PalladiumPincerComplexZ.Wang,X.Feng,W.Fang,T.Tu,Synlett,2011,951-954.Anefficientandsimpleprotocolforphosphine-freeHeckreactionsinwaterinthepresenceofaPd(L-proline)2complexasthecatalystundercontrolledmicrowaveirradiationconditionsisversatileandprovidesexcellentyieldsofproductsinshortreactiontimes.Thereactionsystemminimizescosts,operationalhazardsandenvironmentalpollution.B.K.Allam,K.N.Singh,Synthesis,2011,1125-1131.①SuzukiCouplingTheschemeaboveshowsthefirstpublishedSuzukiCoupling,whichisthepalladium-catalysedcrosscouplingbetweenorganoboronicacidandhalides.Recentcatalystandmethodsdevelopmentshavebroadenedthepossibleapplicationsenormously,sothatthescopeofthereactionpartnersisnotrestrictedtoaryls,butincludesalkyls,alkenylsandalkynyls.Potassiumtrifluoroboratesandorganoboranesorboronateestersmaybeusedinplaceofboronicacids.Somepseudohalides(forexampletriflates)mayalsobeusedascouplingpartners.机理 OnedifferencebetweentheSuzukimechanismandthatoftheStilleCouplingisthattheboronicacidmustbeactivated,forexamplewithbase.Thisactivationoftheboronatomenhancesthepolarisationoftheorganicligand,andfacilitatestransmetallation.Ifstartingmaterialsaresubstitutedwithbaselabilegroups(forexampleesters),powderedKFeffectsthisactivationwhileleavingbaselabilegroupsunaffected.Inpartduetothestability,easeofpreparationandlowtoxicityoftheboronicacidcompounds,thereiscurrentlywidespreadinterestinapplicationsoftheSuzukiCoupling,withnewdevelopmentsandrefinementsbeingreportedconstantly.最近文献StereoconvergentAmine-DirectedAlkyl-AlkylSuzukiReactionsofUnactivatedSecondaryAlkylChloridesZ.Lu,A.Wilsily,G.C.Fu,J.Am.Chem.Soc.,2011,133,8154-8157 RecyclableCatalystsforSuzuki-MiyauraCross-CouplingReactionsatAmbientTemperatureBasedonaSimpleMerrifieldResinSupportedPhenanthroline-Palladium(II)ComplexJ.Yang,P.Li,L.Wang,Synthesis,2011,1295-1301AnEfficientandRecyclableMagnetic-Nanoparticle-SupportedPalladiumCatalystfortheSuzukiCouplingReactionsofOrganoboronicAcidswithAlkynylBromidesX.Zhang,P.Li,Y.Ji,L.Zhang,L.Wang,Synthesis,2011,2975-2983.EfficientPalladium-CatalyzedCross-CouplingReactionofAlkynylHalideswithOrganoboronicAcidsunderAerobicConditionsJ.-S.Tang,M.Tian,W.-B.Sheng,C.-C.Guo,Synthesis,2012,541-546.Ni(COD)2/PCy3CatalyzedCross-CouplingofArylandHeteroarylNeopentylglycolboronateswithArylandHeteroarylMesylatesandSulfamatesinTHFatRoomTemperatureP.Leowanawat,N.Zhang,A.-M.Remerita,B.M.Rosen,V.Percec,J.Org.Chem.,2011,76,9946-9955③NegishiCouplingTheNegishiCoupling,publishedin1977,wasthefirstreactionthatallowedthepreparationofunsymmetricalbiarylsingoodyields.Theversatilenickel-orpalladium-catalyzedcouplingoforganozinccompoundswithvarioushalides(aryl,vinyl,benzyl,orallyl)hasbroadscope,andisnotrestrictedtotheformationofbiaryls. 机理最近文献HighlySelectiveReactionsofUnbiasedAlkenylHalidesandAlkylzincHalides:Negishi-PlusCouplingsA.Krasovskiy,B.H.Lipshutz,Org.Lett.,2011,13,3822-3825.LigandEffectsonNegishiCouplingsofAlkenylHalidesA.Krasovskiy,B.H.Lipshutz,Org.Lett.,2011,13,3818-3821. AnonionicamphiphileenablesasimpleapproachtoPd-catalyzedstereoselectivesp3-sp2cross-couplingsbetweenalkylandalkenylbromidesinthepresenceofzincpowderinwatertogivecoupledproductsingoodyieldswithoutpriorformationoftheorganozincreagents.Thereactionisconductedatroomtemperatureandtoleratesvariousfunctionalgroups.A.Krasovskiy,C.Duplais,B.H.Lipshutz,Org.Lett.,2010,12,4742-4744.Iron-CatalyzedNegishiCouplingTowardanEffectiveOlefinSynthesisT.Niu,W.Zhang,D.Huang,C.Xu,H.Wang,Y.Hu,Org.Lett.,2009,11,4474-4477.HighlyRegio-andStereoselectiveSynthesisof(Z)-TrisubstitutedAlkenesviaPropyneBromoborationandTandemPd-CatalyzedCross-CouplingC.Wang,T.Tobrman,Z.Xu,E.-i.Negishi,Org.Lett.,2009,11,4092-4095.HighlyRegioselectiveSynthesisofTrisubstitutedAllenesviaLithiationof1-Aryl-3-alkylpropadiene,SubsequentTransmetalation,andPd-CatalyzedNegishiCouplingReactionJ.Zhao,Y.Liu,S.Ma,Org.Lett.,2008,10,1521-1523.