C-H活化知识

ActivationofSubstratesinRhodium-CatalyzedC-HFunctionalizationXingweiLiDalianInstituteofChemicalPhysics,ChineseAcademyofSciencesDec.17,20141TheC-HActivationStrategy•Highstep-economy•Readilyavailablehydrocarbons•Broadenedarsenalofretro-syntheticanalysis2M=Pd,Cu,Ni,Co,Rh,Ir,Ru,Mn,Re…Rhodium(III)Catalysisd6,18e-,6-Coordinate•Rh(III)isusuallythehighestoxidationstate.•Cp*Rh(III)islesspronetodecomposition.•WithaCp*ligandandacyclometalatedsubstrate,onlyonecoordinationsiteisavailable.3ObjectivesNewreactionpatternsDifferentselectivitiesHigherreactivityBroadscope/compatibilityGlorius,Adv.Synth.Catal.2014,356,1443.Li,Chem.Soc.Rev.2012,41,3651.SatohandMiura,Chem.Eur.J.2010,16,11212.TwoActivationStrategies4•MoreIonicM+C-Bond•HigherReactivitytowardPolarBonds•Atom-andStep-EconomicSurrogatetoorganoMainGroupReagents•NewPatterns•Generality•ControllableSelectivityPart1:ActivationoftheAreneParticipatingDGs-CoordinatingAbility-Nucleophilicity/Electrophilicity[DGNu/DGE+]-Redox-Reactivity[DGOX]-OtherPost-CouplingTransferability5Shi,Angew.Chem.Int.Ed.2012,51,3948.Cheng,Angew.Chem.Int.Ed.2011,50,4169.Glorius,J.Am.Chem.Soc.2011,133,2154.6InsituGenerationofDGs/ActivationofDGs7DGwithNucleophilicityAngew.Chem.Int.Ed.2012,51,11819.8DGwithNucleophilicity:AzomethineImineMechanisticStudies9KIE=1.211Heterocycles:DifferentSelectivityAngew.Chem.Int.Ed.2012,51,11819.Sulfonamides:MultipleRoles12Angew.Chem.Int.Ed.2012,51,12348.13Sulfonamide:SubstrateScopeAngew.Chem.Int.Ed.2012,51,12348.Mechanism1415ElectrophilicDGs16DGwithRedox-Reactivity:OxidizingN-OGroupAngew.Chem.Int.Ed.2011,50,7791-7796.17Angew.Chem.Int.Ed.2014,53,10794.InternalOxidizingN-ODGsMatsuo,Adv.Synth.Catal.2014,356,1516.Angew.Chem.Int.Ed.2014,53,10794.1920UnpublishedResults21OxidizingC-NBonds:Our1stExample2223collaborationwithProf.YuLanPart2.ActivationofthePolarCouplingPartner24Umpolung:C-HAlkynylation25J.Am.Chem.Soc.2014,136,4780.26J.Am.Chem.Soc.2014,136,4780.Loh,Angew.Chem.Int.Ed.2014,53,2722.ComplementaryScopeinIridiumCatalysis27J.Am.Chem.Soc.2014,136,4780.Path(a)ismorelikely.28Umpolung:C-HAzidationAngew.Chem.Int.Ed.2013,52,11862.OxidativeC-HAzidationAngew.Chem.Int.Ed.2013,53,11862.withFangXieandZisongQi30SyntheticApplicationsofAzideProducts31Umpolung:C-HNitration3233Umpolung:C-HeteroatomFormationActivationbyRingStrain:StrainedOlefins34?氧杂/氮杂苯并降冰片二烯35Angew.Chem.Int.Ed.2013,52,8995.7-Oxabenzonorbornadienes:Redox-NeutralDehydrativeC-CCoupling37Angew.Chem.Int.Ed.2013,52,8995.C-CCouplingwithAziridinesAngew.Chem.,Int.Ed.2013,52,2577.withSongjieYu38MechanisticStudies393-MemberedRings40CouplingDrivenbyAromatization41Org.Lett.2014,16,1586.Summary42Dr.GuoyongSongDr.MiaoZhaoDr.PengZhaoDr.FangXieJinleiChenXueGongFenWangZisongQiYuyeChenXingpingZhangXutingLiXiaohongWeiDongqiWangWencuiZhenXueyunZhangSongjieYuTaoZhangTingtingYangAcknowledgementFundingfromDICP,CAS,andtheNSFC43Prof.YuLan(ChongqingUniversity)