参考案例参考

ChapterChapterReduction11.Conceptionand1.Conceptionand+--+-2+HH--+e.-+R2RRRRRR二RRO+HH--+e.-+R2RRRRRR二RROOOHOH3-Catalytic(LiAlHNaBHBCatalytic(LiAlHNaBHB)44 metalreduction(Na-Li-AcOH,Fe,Mg4CatalyticHeterogenous（非均相催化氢CatalyticHeterogenous（非均相催化氢化/多相催化非均相催催化剂：Pt,Raney-Pt,Pd:吸附在载体特点：活性高，根据底物不同，可在常温，常压下反应；也可在高温、高压下反应。含硫化合物会使其中毒失活缺点：很贵，5不同功能团氢化难易程度Functional HydrogenationRCRCN易(Z-RCH不同功能团氢化难易程度Functional HydrogenationRCRCN易(Z-RCH2OH+难RR62.2Homogenoushydrogenation(均相催化氢化2.2Homogenoushydrogenation(均相催化氢化RhRu的络合物(TTC);(PPh3)3常优点均相反应，溶解度好，收率明显提高，室温、常压反应；改变不同的配体，可得到不同性能的催化剂，在不对称7883.MetalHydride3.MetalHydride9AluminumHydrideReducinglessAluminumHydrideReducinglessreactive,more---Lithium-LithiumtrialkoxyaluminumhydridescanbeBorohydrideReducingBorohydrideReducing-NaBH4requiresactivationofthecarbonylby-NaBH4requiresactivationofthecarbonylbyhydrogen-bondingwithalcoholicsolventforreductions.ThereforethereactionsareruninalcoholicThereagentslowlyreactswithMeOH(30min)>EtOH(slow)>iPrOH(stable)>tBuOHSolventsformetalhydrideSolventsformetalhydrideMetalhydrideEther,THF,diglymeTHF,diglymeBen,Tol,XyleneW,ethanol,diglymeW,methanol,DMSOTHF,diglymeEther,THFToluene,[DIBAL-ProductsofProductsofmetalhydridea.Reductionproceedstothealdehydestageonly;b.veryslowc.Reductonproceedstolactolstageonly;d.phenylestersgivee.Someamidesarereducedtoaldehydes;f.whereRisaliphatic;ifRisaromatic,Azoarenesareformed;1g7.X=halogenorOSO2R’.ReactionsofReactionsofBoraneCharacteristicsofHydrideReducingCharacteristicsofHydrideReducingDIBAL-GarnerOrg.Syn.1992,70,GarnerOrg.Syn.1992,70,-Good-GoodforWeinrebamidetoOPhCH2NH2,OOOOMeCN,r.t,NaBH3CN,Or.t,6nNNpiperadine,OPhCH2NH2,OOOOMeCN,r.t,NaBH3CN,Or.t,6nNNpiperadine,MeOH,r.t,NReview:NarasimhanAldrichim.Acta1998,31,ReagentcomparisionsReagentcomparisionsfor1,2-vs.1,4---Selectivereductionof-Butwillalsoreduceolefins,allylicalcohols,andLiBHEt3(SuperLiBHEt3(Super4.Dissolving4.DissolvingmetalActivemetals:Li,Na,K,Mg,Ca,Zn,Sn,Protondonor:water,ethanol,BirchRR给电子基 Li,- 吸电子基BirchRR给电子基 Li,- 吸电子基-LiquidNH3(bp–33-LiquidNH3(bp–33oC)isusedtodissolvemetal,ethercosolvent(Et2OorTHF)isusedtodissolvesubstrate,andaprotonsourcetBuOH;EtOH;MeOH;isusedtoquenchthereaction.-Ifprotonsourceisc.HHHHH.-.-HHHHHHH-Ifprotonsourceisc.HHHHH.-.-HHHHHHHd.d.DissolvingMetalCarbonylDissolvingMetalCarbonylKetone-Review:ComprehensiveOrg.Syn.,Vol.8,Acyloin 甲苯CO2O苯Acyloin 甲苯CO2O苯Radical-Radical-ReductiveReductiveAsymmetricAsymmetricCatalyticAsymmetricAsymmetricCatalyticHydrogenationofC=CAsymmetricCarbonylAsymmetricReductionofAsymmetrictransferAsymmetricCatalyticHydrogenationofC=C1.ChiralPhosphineRNPRRRNNPPhPR2Mec-MePP(AsymmetricCatalyticHydrogenationofC=C1.ChiralPhosphineRNPRRRNNPPhPR2Mec-MePP(S,S)-CHORAPHOS(R,R)-DIPAMP 2(S,S)-(R,R)-3R)-NN22PPPPRMeNPPR=c-C5H9,c-t-Bu,CEt3,1-adamantylNXXPO 2(S,S)-(R,R)-3R)-NN22PPPPRMeNPPR=c-C5H9,c-t-Bu,CEt3,1-adamantylNXXPO(R)-BIPHEMP,R=Ph,X=Me(R)-BIPHER,R=c-Hex,X=MeMeOBIPHEP,R=Ph,X=OMe2.Enantioselectivehydrogenationsof-acylaminoacrylicacidderivatives(2.Enantioselectivehydrogenationsof-acylaminoacrylicacidderivatives(潜手性-氨基丙烯- H2, Chiral NHAcEnantioselectivehydrogenationsEnantioselectivehydrogenationsof-acylaminoacrylicacidstothecorrespondingaminoacidsSpirophosphinite-catalyzedSpirophosphinite-catalyzed3.Asymmetric3.AsymmetricCatalyticHydrogenationofAcrylicAcidsandDerivatives.Hayashi,T.;Kawamura,N.;Ito,Y.Hayashi,T.;Kawamura,N.;Ito,Y.J.Am.Chem.Soc.1987,109,4.Asymmetric4.AsymmetricHydrogenationofEnolAsymmetrichydrogenationAsymmetrichydrogenationofethynyl5.AsymmetricHydrogenation5.AsymmetricHydrogenationofUnfunctionalizedAshasbeendiscussedthusfar,mostofthesubstrateshavepolarfunctionalgroups.Examplesoftheasymmetrichydrogenationofunfunctionalizedolefineswithhighenantioselectivityarerare.AsymmetricHydrogenationAsymmetricHydrogenationofUnfunctionalized7.Examplesof7.ExamplesofPotentialIndustrialNoyori,R.J.Am.Chem.Soc.1987,109,AsymmetricCarbonylStoichiometricReagentsAsymmetricCarbonylStoichiometricReagentsforAsymmetricCarbonylReductions(N-甲基麻黄-BINAL--BINAL-NoyoriJ.Am.Chem.Soc.1984,NoyoriJ.Am.Chem.Soc.1984,106,BogerJ.Am.Chem.Soc.1998,120,Acetylenicketoneorolefinicketone R2R2HHOAcetylenicketoneorolefinicketone R2R2HHOHR2 R1R1OH-Midland-MidlandJ.Org.Chem.1989,54,BrownJ.Org.Chem.1989,54,2.TransitionMetal-ComplexCatalyzedHydrogenation2.TransitionMetal-ComplexCatalyzedHydrogenationofCarbonylCompounds-BINAP- (R)- (S)-AsymmetricReductionofAsymmetricReductionoffunctionalizedExampleExampleAsymmetrichydrogenationofOORu-(R)-ExampleAsymmetrichydrogenationofOORu-(R)-or-(S)-HCl,(R,(S,>99.9%yield>ExampleEnantioselectiveExampleEnantioselectiveHydrogenationReactionsofMethyl3-AsymmetricReductionAsymmetricReductionofsimpleIncontrasttotheirsuccessintheasymmetrichydrogenationoffunctionalizedketones,BINAP-RucatalystsfailtogivegoodresultswithsimpleketonebecausesuchsubstrateslackheteroatomsthatenablethesubstratetoanchorstronglytotheRumetal.R=Me,97%eeandR=Me,97%eeand>99%Proposedmechanismforweak-base-promotedRh-catalyzedasymmetrichydrogenation.Proposedmechanismforweak-base-promotedRh-catalyzedasymmetrichydrogenation.HH Cl Cl Rh OHSRO-, Cl Rh ROH,SorAsymmetricHydrogenationAsymmetricHydrogenationofSimpleKetonesCatalyzedbyRh-PennPhosO0.25mol%RuCl2(p-2.5mol%i-PrOK/i-O0.25mol%RuCl2(p-2.5mol%i-PrOK/i-时间e.e.n-n-3TheOxazaborolidineCatalystSystem硼杂噁唑烷催化体系1981,Hirao;Corey,CBS催化剂(Corey-Bakshi-HHHOOONNNRO4aR=4bR=1aR=1bR=1cR=2HH3TheOxazaborolidineCatalystSystem硼杂噁唑烷催化体系1981,Hirao;Corey,CBS催化剂(Corey-Bakshi-HHHOOONNNRO4aR=4bR=1aR=1bR=1cR=2HH ONO BN6aR=6bR=75aR=5bR=5cR=n-Representativeoxazaborolidinesfortheasymmetricreductionofprochiral (S)- (R1R2CH1min.,25 (S)- (R1R2CH1min.,252RR+ 3TheproposedmechanismforCBScatalyzedHHOONNBBOHHHHONOBOH3NBHHHTheproposedmechanismforCBScatalyzedHHOONNBBOHHHHONOBOH3NBHHHThekeyThekeystepinvolvestheenantioselectivereductionof-chloropropiophenone88withCBScatalysttoyieldcompound89withover99%yieldand94%ee.--Pinene --Pinene (+)- (-)-AsymmetricReductionAsymmetricReductionofProchiralKetonesUsing10mol%of(+)-1-Chiral-amino-Chiral-aminoTetrahedronAsymmetry1993,4,TetrahedronLett.1995,36,UsefulcompoundsUsefulcompoundsforketoneAsymmetricReductionof-RhodiumcatalyzedAsymmetricReductionof-RhodiumcatalyzedBurk,M.J.;Feaster,J.E.J.Am.Chem.Soc.1992,114,H NOR RDuPHOSOneproblemforOneproblemfortheasymmetrichydrogenationofInterconversionof(Z)/(E)isomersofanTetrahedronLett.1990,31,-Chiraltitanocene-Chiraltitanocene12hoursatroomtemperature,with97%eeandupto5000turnovers.Theimportantfeatureofthisreactionsystemisitsexperimentalsimplicity,highyieldandpurityaswellasveryhighenantioselectivity.55%conversionand47%eewithprolongedreactiontime(96hours).Primary55%conversionand47%eewithprolongedreactiontime(96hours).PrimaryamineshavethemostpronouncedeffectontheThedrawbackofthisreactionisitsextremelyhighsensitivitytothestericbulkofthenitrogensubstitutent.EffectofEffectofaddedamineonimineAsymmetrictransferAsymmetrictransfer-Meerwein-Ponndorf-Verleyreaction(MPVRuthenium-Ruthenium-RecentRecentDevelopmentAMetal-FreeTransferHydrogenation:OrganocatalyticConjugateReductionAMetal-FreeTransferHydrogenation:OrganocatalyticConjugateReductionof,-UnsaturatedJungWoonYang,MariaT.HechavarriaFonseca,NicolaVignola,andBenjaminList*Received:August28,Angew.Chem.Int.Ed.2004,43,6660CatalystscreeningCatalystscreeningfortheiminiumcatalyticconjugatereductionof,-unsaturatedaldehydes.OrganocatalyticconjugateOrganocatalyticconjugatereductionof,-unsaturatedProposedmechanismProposedmechanismofiminiumInsummary,wehavedevelopedthefirstmetal-freeInsummary,wehavedevelopedthefirstmetal-freecatalytictransferhydrogenation.Thisnoveliminiumcatalyticconjugatereductionof,-unsaturatedaldehydesishighlyefficientandchemoselective.Itrequireslowcatalystloadingsandtoleratesvariousfunctionalgroupsthataresensitivetotheconditionsofstandardhydrogenationsandalternativeconjugatereductions.Metal-Free,OrganocatalyticAsymmetricTransferHydrogenationofUnsaturatedAldehydes**JungMetal-Free,OrganocatalyticAsymmetricTransferHydrogenationofUnsaturatedAldehydes**JungWoonYang,MariaT.HechavarriaFonseca,NicolaVignola,andBenjaminList*Received:October26,Angew.Chem.Int.Ed.2005,44,108OrganocatalyticasymmetricOrganocatalyticasymmetrictransferhydrogenation,-unsaturatedProposedmechanismoftheorganocatalyticasymmetrictransferhydrogenation.Proposedmechanismoftheorganocatalyticasymmetrictransferhydrogenation.AttractivefeaturesofAttractivefeaturesofthisHighyields,chemo-andSimplicityandEnantioselectiveOrganocatalyticHydrideReductionSte´phaneEnantioselectiveOrganocatalyticHydrideReductionSte´phaneG.Ouellet,JamisonB.Tuttle,andDavidW.C.DiVisionofChemistryandChemicalEngineer