C-H活化知識(shí)ppt課件

ActivationofSubstratesinRhodium-CatalyzedC-HFunctionalization,XingweiLiDalianInstituteofChemicalPhysics,ChineseAcademyofSciences,Dec.17,2014,1,TheC-HActivationStrategy,Highstep-economyReadilyavailablehydrocarbonsBroadenedarsenalofretro-syntheticanalysis,M=Pd,Cu,Ni,Co,Rh,Ir,Ru,Mn,Re,2,Rhodium(III)Catalysis,d6,18e-,6-CoordinateRh(III)isusuallythehighestoxidationstate.Cp*Rh(III)islesspronetodecomposition.WithaCp*ligandandacyclometalatedsubstrate,onlyonecoordinationsiteisavailable.,ObjectivesNewreactionpatternsDifferentselectivitiesHigherreactivityBroadscope/compatibility,Glorius,Adv.Synth.Catal.2014,356,1443.Li,Chem.Soc.Rev.2012,41,3651.SatohandMiura,Chem.Eur.J.2010,16,11212.,3,TwoActivationStrategies,MoreIonicM+C-BondHigherReactivitytowardPolarBondsAtom-andStep-EconomicSurrogatetoorganoMainGroupReagents,NewPatternsGeneralityControllableSelectivity,4,Part1:ActivationoftheArene,ParticipatingDGs-CoordinatingAbility-Nucleophilicity/ElectrophilicityDGNu/DGE+-Redox-ReactivityDGOX-OtherPost-CouplingTransferability,Shi,Angew.Chem.Int.Ed.2012,51,3948.,Cheng,Angew.Chem.Int.Ed.2011,50,4169.,Glorius,J.Am.Chem.Soc.2011,133,2154.,5,InsituGenerationofDGs/ActivationofDGs,6,DGwithNucleophilicity,7,Angew.Chem.Int.Ed.2012,51,11819.,DGwithNucleophilicity:AzomethineImine,8,MechanisticStudies,9,KIE=1.2,10,Heterocycles:DifferentSelectivity,Angew.Chem.Int.Ed.2012,51,11819.,11,Sulfonamides:MultipleRoles,Angew.Chem.Int.Ed.2012,51,12348.,12,Sulfonamide:SubstrateScope,Angew.Chem.Int.Ed.2012,51,12348.,13,Mechanism,14,ElectrophilicDGs,15,DGwithRedox-Reactivity:OxidizingN-OGroup,Angew.Chem.Int.Ed.2011,50,7791-7796.,16,Angew.Chem.Int.Ed.2014,53,10794.,17,InternalOxidizingN-ODGs,Matsuo,Adv.Synth.Catal.2014,356,1516.,Angew.Chem.Int.Ed.2014,53,10794.,18,19,UnpublishedResults,20,OxidizingC-NBonds:Our1stExample,21,22,collaborationwithProf.YuLan,23,Part2.,ActivationofthePolarCouplingPartner,24,Umpolung:C-HAlkynylation,J.Am.Chem.Soc.2014,136,4780.,25,J.Am.Chem.Soc.2014,136,4780.,Loh,Angew.Chem.Int.Ed.2014,53,2722.,26,ComplementaryScopeinIridiumCatalysis,J.Am.Chem.Soc.2014,136,4780.,27,Path(a)ismorelikely.,28,Umpolung:C-HAzidation,Angew.Chem.Int.Ed.2013,52,11862.,29,OxidativeC-HAzidation,Angew.Chem.Int.Ed.2013,53,11862.,withFangXieandZisongQi,30,SyntheticApplicationsofAzideProducts,31,Umpolung:C-HNitration,32,Umpolung:C-HeteroatomFormation,33,ActivationbyRingStrain:StrainedOlefins,?,氧雜/氮雜苯并降冰片二烯,34,Angew.Chem.Int.Ed.2013,52,8995.,35,36,7-Oxabenzonorbornadienes:Redox-NeutralDehydrativeC-CCoupling,Angew.Chem.Int.Ed.2013,52,8995.,37,C-CCouplingwithAziridines,Angew.Chem.,Int.Ed.2013,52,2577.,withSongjieYu,38,MechanisticStudies,39,3-MemberedRings,40,CouplingDrivenbyAromatization,Org.Lett.2014,16,1586.,41,Summary,42,Dr.GuoyongSongDr.MiaoZhaoDr.PengZhaoDr.FangXieJinleiChenXueGongFenWangZisongQiYuyeChen,XingpingZhangXutingLiXiaoh