不对称催化环氧化研究进展

204200512JOURNALOFSOUTHWESTUNIVERSITYOFSCIENCEANDTECHNOLOGYVol.20No.4Dec.2005:2005-05-09(621000):Ti(O-i-Pr)4-DETSalen,Sharpless;Jacobsen,;;::O621.3+4:A:1671-8755(2005)04-0068-08DevelopmentofAsymmetricCatalyzingEpoxidationLiuSiman(DepartmentofChemistry,MianyangNormalUniversity,Mianyang621000,Sichuan,China)Abstract:Catalysissystemsusedinasymmetriccatalyzingepoxidationwerereviewed.Thesesystemsin2cludeTi(O-i-Pr)4-DETreagent,chiralSalensystem,chiralacetonereagent,loadedchiralcatalyst,andsoon.Theirpropertiesincatalyzingepoxidationwasdiscussed,too.Sharplessisafacile,easyoperatedandhighenantio-selectivitycatalyst;Jacobsencatalysthaspromisingindustrialapplication;chiralacetonereagentisprosperousindecreasingpollutionofheavymetal;loadedcatalystiseasyrecycledandpurifiedforindustrialvalue.Keywords:chiral;asymmetric;epoxidation;enantio-selectivity,,,1960,(thalidomide),,1965S-,R-,19923,,,,,,,,,SharplessJacobs2en[14]1Ti(O-i-Pr)4-DET1980Sharpless[1],[2],[(Ti(O-i-Pr)4](DET)5%10%,,e.e.90%,S-[3],ARCO(Ti(O-i-Pr)4):L-(+)-D-(-)-(DET)=2:2.4(TBHP):L-D-DET,O2,-,(Ti(O-i-Pr)4):(DET)[4][56],,,,(leukotrienederivatives)[7](maytansine)[8][9],Sharpless,,,2SalenSharplessJacobsen,Schiffbase,Salen-Mn()[10],,93%,e.e.93%964:,Katsuki[11]SalenMn(III)1994Jacobsen[12]SchiffMn(III),13%NaClO,CH2Cl2,PhCH=CHCOOEt,1996KatsukiSchiffMn(III),Mukaiyama[13],,101.325kPa,SchiffMn(III),e.e%60%70%072005[1415],:1,2-,:X=H,tBu,OMe;X’=H,Me,tBu,OMe,OSii-Pr3,CrCoMoW[16]Jacobsen[17],e.e.,-N-[1819][20](),e.e.4,6-,NaOCl,--N-67%,98%,e.e.,93%Kochi[21]-N-,Ja2cobsen-[15]Pietik¾inen[22],H2O2,,,H2O2HO2-,Mn()Mn()-O-OH,,Jacobsen,[20][19][23],,31984,Curci[24],[2527]KHSO5,dioxirane,,:YianShi[28]D-1,174:,pHpH78,,10%,pH1113,80%,e.e.[29]80%pH=12,OH-[30]:,2Baeyer-Viliiger;pH,,23,,()CH3CN(1:2,V/V),--,88%,e.e.94%DanYang[30]R-7,e.e.8Cl9,,-1,2-,85%e.e.,32%e.e.,,,,,,4Jacobsen,,,4:1)Salen,,[31]2)MCM-41,272005[32]3)Salen,,4)Salen[33],Jan2da[34]JandaJelSalen-Mn,,,,e.e.88%,3,,,,,2090,,,5,P.Page[35],-N-,KHSO5,-,78%,e.e.73%Juli[36]19802004,Militzer,TBAB[37];,,[38]K.Mikami1997(asymmetricactivation)Nature[39],,,aldolDiels-Alder[40],,,P-450,,Jacobsen,,6Ti(O-i-Pr)4-ETSalen,,,,,,1Katsuki,T.andSharpless,K.B.TheFirstPracticalMethodforAsymmetricEpoxidation[J].J.Am.Chem.Soc.,1980,102(18):59745976374:2Gao,Y.andSharpless,K.B.CatalyticAsymmetricEpoxidationandKineticResolution:ModifiedProceduresIncludinginSituDerivatization[J].J.Am.Chem.Soc.,1987,109(19):576557803Klunder,J.M.,Onami,T.andSharpless,K.B.ArenesulfonateDerivativesofHomochiralGlycidol:VersatileChiralBuildingBlocksforOrganicSynthesis[J].J.Org.Chem.,1989,54(6):129513044Lu,L.D.,Johnson,R.A.,Finn.M.G.,andetal.TwoNewAsymmetricEpoxidationCatalysts.UnusualStoichiometryandInverseEnantiofacialSelection[J].J.Org.Chem.,1984,49(4):7287315Wang,Z.M.,Zhou,W.S.andLin,G.Q.EffectofMetalHydrideandSilicaGelontheSharplessAsymmetricEpoxidation[J].TetrahedronLett.,1985,26(50):622162246Wang,Z.M.andZhou,W.S.AsymmetricEpoxidationofAllylicAlcoholbytheModifiedSharplessReagent[J].Tetrahedron,1987,43(13):293529447Corey,E.J.andHashimoto,S.ChirallyDirectedSynthesisof(-)-methyl5(S),6(S)-oxido-7-hydroxyheptanoate,aKeyIntermediatefortheTotalSynthesisofLeukotrienesA,C,DandE,A.E.Barton[J].J.Am.Chem.Soc.,1981,103(3):7217228Meyers,A.I.andHudspeth,J.P.EnantioselectiveSynthesisofC3-C10Fragment(NortheasternZone)ofMaytansinoidswith4-chiralCenters(4S,5S,6R,7S)[J].TetrahedronLett.,1981,22(40):392539289Mori,K.andUeda,H.SynthesisoftheOpticallyActiveFormsof2,6-dimethyl-1,5-heptadien-3-olAcetate,thePhero2moneoftheComstockMealybug[J].Tetrahedron,1981,37(15):2581258310Zhang,W.,Loebach,J.L.,Wilson,S.R.andetal.EnantioselectiveEpoxidationofUnfunctionalizedOlefinsCatalyzedbySalenManganeseComplexes[J].J.Am.Chem.Soc.,1990,112(7):2801280311Irie,R.,Noda,K.,Ito,Y.andetal.CatalyticAsymmetricEpoxidationofUnfunctionalizedOlefins[J].TetrahedronLett.,1990,31(50):7345734812Jacobsen,E.N.andDeng,L.EnantioselectiveCatalyticEpoxidationofCinnamateEsters[J].Tetrahedron,1994,50(15):4323433413Yamada,T.,Imagawa,K.,Nagata,T.andetal.EnantioselectiveEpoxidationofUnfunctionalizedOlefinswithMolecularOxy2genandAldehydeCatalyzedbyOpticallyActiveManganese(III)Complexes[J].Chem.Lett.,1992,11:2231223414Zhang,W.andJacobsen,E.N.AsymmetricOlefinEpoxidationwithSodiumHypochloriteCatalyzedbyEasilyPreparedChiralManganese(III)SalenComplexes[J].J.Org.Chem.,1991,56(7):2296229815Jacobsen,E.N.,Zhang,W.andGler,M.L.ElectronicTuningofAsymmetricCatalysts[J].J.Am.Chem.Soc.,1991,113(17):6703670416Wang,X.Y.,Shi,H.C.,Sun,C.andetal.AsymmetricEpoxidationofCis-1-propenylphosphonicAcid(CPPA)Cata2lyzedbyChiralTungsten(VI)andMolybdenum(VI)Complexes[J].Tetrahedron,2004,60(48):109931099817Palucki,M.,Finney,N.S.,Pospisil,P.J.andetal.TheMechanisticBasisforElectronicEffectsonEnantioselectivityinthe(salen)Mn(III)-CatalyzedEpoxidationReaction[J].J.Am.Chem.Soc.,1998,120(5):94895418Jacobsen,E.N.,Deng,L.,Furukawa,Y.andetal.EnantioselectiveCatalyticEpoxidationofCinnamateEsters[J].Tetra2hedron,1994,50(15):4323433419Brandes,B.D.andJacobsen,E.N.HighlyEnantioselective,Ca