ChapterChapterReduction11.Conceptionand1.Conceptionand+--+-2+HH--+e.-+R2RRRRRR二RRO+HH--+e.-+R2RRRRRR二RROO3-Catalytic(LiAlHNaBHBCatalytic(LiAlHNaBHBH44 (Na-AcOH,Fe,Mg4CatalyticHeterogenous（多相催化非均相催CatalyticHeterogenous（多相催化非均相催Raney-Pt,Pd:含硫化合物會使其中毒失活5Functional HydrogenationRCCRRCNRCH=CHR(Z-易Functional HydrogenationRCCRRCNRCH=CHR(Z-易RCH2OH+難RR62.2Homogenoushydrogenation均相催化氫化2.2Homogenoushydrogenation均相催化氫化RhRu(TTC);(PPh3)3常優(yōu)用：(PPh3)3點改變不同的配體，可得到不同性能的催化劑，在不對稱7883.MetalHydride3.MetalHydride9AluminumHydrideReducinglessAluminumHydrideReducinglessreactive,more---Lithium-LithiumtrialkoxyaluminumhydridescanbeBorohydrideReducingBorohydrideReducing-NaBH4requiresactivation-NaBH4requiresactivationofthecarbonylbyhydrogen-bondingwithalcoholicsolventforreductions.ThereforethereactionsareruninalcoholicThereagentslowlyreactswithMeOH(30min)>EtOH(slow)>iPrOH(stable)>tBuOHSolventsformetalhydrideSolventsformetalhydrideMetalhydrideEther,THF,diglymeTHF,diglymeBen,Tol,XyleneW,ethanol,diglymeW,methanol,DMSOTHF,diglymeEther,THFToluene,[RED-[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給電子 CO2H吸電子BirchRR給電子 CO2H吸電子-LiquidNH-LiquidNH3(bp–33oC)isusedtodissolvemetal,ethercosolvent(Et2OorTHF)isusedtodissolvesubstrate,andaprotonsourcetBuOH;EtOH;MeOHisusedtoquenchthereaction.-Ifprotonsourceisc.HHHHH.-.-HHHHHHH-Ifprotonsourceisc.HHHHH.-.-HHHHHHHd.d.DissolvingMetalCarbonylDissolvingMetalCarbonylKetone-Review:ComprehensiveOrg.Syn.,Vol.8,Acyloin 甲CO2O苯Acyloin 甲CO2O苯AsymmetricAsymmetricAsymmetricAsymmetricCatalyticHydrogenationofC=CAsymmetricCarbonylAsymmetricReductionofAsymmetrictransferAsymmetricCatalyticHydrogenationofC=CChiralPhosphineR PRRRNNP2RDuPHOSDEGHOSFe2PPOPHOSNORPHOSMec-MePPAsymmetricCatalyticHydrogenationofC=CChiralPhosphineR PRRRNNP2RDuPHOSDEGHOSFe2PPOPHOSNORPHOSMec-MePP(S,S)-CHORAPHOSCYCPHOS(R,R)- 2(S,S)-Ph22(R)-(+)-(R,R)-3R)-NN(-)-22PPPPRNPPR=c-C5H9,c-t-Bu,CEt3,1-NXXPP 2(S,S)-Ph22(R)-(+)-(R,R)-3R)-NN(-)-22PPPPRNPPR=c-C5H9,c-t-Bu,CEt3,1-NXXPP(R)-BIPHEMP,R=Ph,X=Me(R)-BIPHER,R=c-Hex,X=MeMeOBIPHEP,R=Ph,X=OMe2.Enantioselectivehydrogenationsof-acylaminoacrylicacidderivatives2.Enantioselectivehydrogenationsof-acylaminoacrylicacidderivatives(潛手性-氨基丙-氨基 H2, Chiral EnantioselectivehydrogenationsEnantioselectivehydrogenationsof-acylaminoacrylicacidstothecorrespondingaminoacidsSpirophosphinite-catalyzedSpirophosphinite-catalyzed3.Asymmetric3.AsymmetricCatalyticHydrogenationofAcrylicAcidsandDerivatives.Hayashi,T.;Kawamura,Hayashi,T.;Kawamura,N.;Ito,Y.J.Am.Chem.Soc.1987,109,4.Asymmetric4.AsymmetricHydrogenationofEnolAsymmetrichydrogenationAsymmetrichydrogenationofethynyl5.AsymmetricHydrogenation5.AsymmetricHydrogenationofUnfunctionalizedAshasbeendiscussedthusfar,mostofthesubstrateshavepolarfunctionalgroups.Examplesoftheasymmetrichydrogenationofunfunctiona