金催化炔烃环异构化6-endo-dig-cyclization-of-N-propargylaminoquinone课件

N-炔丙胺基醌的6-endo-dig亲电性成环反应研究报告人:王少仲副教授南京大学化学化工学院2011年11月14日Contents1. Au(I)-Catalyzed6-endo-digCycloisomerizationofN-Propargylaminoquinones2. Iodine-Induced6-endo-digElectrophilicCyclizationofN-Propargylaminoquinones3. CuCl2-Promoted6-endo-digChlorocyclizationofN-Propargylaminoquinones

4. Au(I)-CatalyzedCascadeReactionofN-PropargylaminoquinonesInitialDesignPossiblePathwaysAu(I)-Catalyzed6-endo-digCycloisomerizationX-RayCrystalStructure

of2aOptimizationofReactionConditionsentryconditionyield(%)110mol%Ph3PAuOTf,PhCH3,100oC,6h82210mol%Ph3PAuOTf,THF,60oC,12h19310mol%Ph3PAuOTf,HOAc,100oC,1h85410mol%PtCl2,HOAc,100oC,2h49510mol%NaAuCl4,HOAc,100oC,4h34610mol%CuBr,HOAc,100oC,4h14710mol%AgOTf,HOAc,80oC,12h0810mol%Ph3PAuCl,HOAc,100oC,4h19SubstrateScopeSubstrateScopeProposedMechanismAzaanthraquinoneAlkaloidsPentacyclicAlkaloidsBearingAzaanthraquinoneMoietyClassicMethodologytoAzaanthraquinoneIodine-Induced6-endo-digElectrophilicCyclizationOptimizationofReactionConditionsentryconditionYield(%)1I2,NaHCO3,CH2Cl2,rt,12h422I2,NaHCO3,CH3CN,80oC,12h563I2,NaHCO3,dioxane,100oC,12h404I2,NaHCO3,CH3NO2,100oC,4h775I2,Na2CO3,CH3NO2,100oC,4h606I2,K2CO3,CH3NO2,100oC,4h567I2,K3PO4,CH3NO2,100oC,4h60Electrophile:3.0equiv;Base:2.0equivSubstrateScopeSubstrateScopeX-RayCrystalStructure

of3e.CH3CNCuCl2-Promoted6-endo-digChlorocyclizationOptimizationofReactionConditionsentryconditionayld(%)15mol%Pd(OAc)2,LiCl,HOAc,80oC,4h025mol%Pd(OAc)2,CuCl2,HOAc,80oC,1h5035mol%Pd(OAc)2,CuCl2,DMA,80oC,4h1745mol%Pd(OAc)2,CuCl2,CH3CN,80oC,1h6055mol%Pd(OAc)2,CuCl2,CH3NO2,80oC,1h6665mol%Pd(OAc)2,FeCl3,CH3NO2,80oC,1h071.0equivCuCl2,CH3NO2,80oC,1h85aCompound1aassubstrateandtheamountofchlorinesourceis3.0equivX-RayCrystalStructure

of4aSubstrateScopeSubstrateScopeProposedMechanismPreparationof3-ClorosampangineCuCl2-PromotedCascadeCyclizationAu(I)-CatalyzedCascadeReaction

OptimizationofReactionConditionsentryconditionYield(%)15mol%Ph3PAuOTf,HOAc,100oC,2h025mol%Ph3PAuOTf,TFA,rt,1h9035mol%Ph3PAuSbF6,TFA,rt,1h8545mol%Ph3PAuNTf2,TFA,rt,1h7555mol%Ph3PAuClO4,TFA,rt,2h7065mol%Ph3PAuCl,TFA,60oC,1h9075mol%NaAuCl4.2H2O,TFA,60oC,2h608TFA,60oC,2h0SubstrateScopeProposedMechanismSummaryAcknowledgementJiang,Chunhui