金属卟啉催化烯烃环氧化及反应机理研究-李臻

　　:20017,:20023　*(29773056,29933050)**　e-mail:[e-mail]金属卟啉催化烯烃环氧化及反应机理研究*李　臻　夏春谷**(中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室　兰州730000,China)　　本文就铁卟啉及锰卟啉模拟酶体系近年来在催化烯烃环氧化反应机理方面的最新研究成果进行了详细阐述。均相催化剂固载化技术的应用,使金属卟啉配合物担载于无机载体上克服了卟啉的二聚、催化剂再生等难题,有力地推动了金属卟啉配合物应用研究的发展。　金属卟啉　反应机理　中间体　担载:O641.4;O643.3　:A　:1005-281X(2002)05-0384-07ReviewonMechanismofAlkeneEpoxidationbyMetalloporphyrinsLiZhen　XiaChungu**(StateKeyLaboratoryofOxoSynthesisandSelectiveOxidation,LanzhouInstituteofChemicalPhysics,TheChineseAcademyofSciences,Lanzhou730000,China)Abstract　Newresearchesonmechanismofalkeneepoxidationbyironporphyrinsandmanganesepor-phyrinsinrecentyearsarepresentedinthispaper.Immobilizationofmetalloporphyrinsoverinorganicsupporterhasmanyadvantagessuchaspreventionofintermolecularreactionandeasyrecoveryofthecata-lysts.Thisacceleratesthedevelopmentofstudiesonmetalloporphyrinsapplications.Keywords　metalloporphyrins;reactionmechanism;intermediates;support、　。,、cP-450;。。、、、[1,2],、、、、、。,,。,,,,,。,,,;,。,,。、P-450P-450,Fe(Ⅱ),14520029化　学　进　展PROGRESSINCHEMISTRYVol.14No.5　Sep.,2002,。1　P-450P-450(1),Fe(Ⅴ)O,,、、、。(PhIO,H2O2),P-450。7080,,P-450,。:(1)P-450、,。(2)P-450。①、;②;③、。、,。,:①,O2、PhIO、ClO-、H2O2、ROOHIO-54;②();③[3]。,。,FeⅣ(O)(Por.)+·1,,[3—5]。Watanabe-40℃CH2Cl2Fe(TMP)ClPhIO1,F5PhIO(pentafluoroiodosylben-zene)1[6],,Fe(Ⅲ)porphyrinPhIOPhIO-Fe(Ⅲ)porphyrin。2　1O—OH2O2tert-,O—O。Tray-lor[7,8]CH2Cl2/CH3OH,1O—O2(2,A)。Bruice1O—O3()(2,B)[9,10],3[11]。·385·5　　3　O—O2H2O2tert-O—O20,。O—OH2O2[7—10]。1O—O2(2,AD);3(2,BE)。Traylor(2,AC),tert-Fe(TMP)ClPFIBm-CPBA[7,12]。,FeⅣ(O)(Por.)+·,[6,13—19]。,Nam[20]Fe(TPFPP)Cl、Fe(TDFPP)ClFe(TDCPP)ClH2O2、tert-butylhydroperoxide(t-BuOOH)m-CPBA,、21O—O2(A);,1O—O,12。,()O—O。Nam[21](4)H2O2、t-BuOOH、MPPHm-CPBA,m-CPBA,,;H2O2t-BuOOH,(4a4b)O—O,4e4fO—O。,,t-BuOOHMPPHO—O,m-CPBAO—O。Iron(Ⅲ)porphyrinsXYZ4a.Fe(TF4TMAP)(OTf)5FFN+(CH3)34b.Fe(TPFPP)ClFFF4c.Fe(TDFPP)ClFHH4d.Fe(TDCPP)ClClHH4e.Fe(TPP)ClHHH4f.Fe(TMP)ClCH3HCH34　　　,H2O2(Por.)FeⅢ—OORO—O?NamH2O2e*dxz,dyzdz2,O—Oσ*,H2O2。,Nam[22]FeⅣ(O)(Por.),CH2Cl2tolueneX-=Cl-、F-、CH3CO-2OH-,Fe(TMP)XPhIOFeⅣ(O)(Por.),X-=CF3SO-3、ClO-4NO3-FeⅣ(O)(Por.)+·,70%。,toluenem-CPBAFe(TMP)X,X-CF3SO-3、ClO-4NO-3,O—OFeⅣ(O)(TMP)+·,X-OH-CH3CO-2O—O(TMP)FeⅢN—O。Nam[23]Fe(TMP)ClH2O2,5-Cl-1-MeIm(5--1-),·386·化　学　进　展145　H2O2e*dxz,dyzdz2[21],,,(Por.)FeⅢ-OOH(Por.)FeⅢ—HOOH,,。、,PhIO,,,,,,。,,(:),MnVO,,。Thellend[24]Mn(TDCPP)ClH2O2,,H2O2PhIO、ClO-。Arasasingham[25](Cl8TPP)MnⅣ(O),,6。(Cl8TPP)(B)MnⅤ(O)(B=),MnⅣ(O),。,MnⅢ6　MnⅣ(O)(Por.)Cl(Por.=TPP、TMOPP、TPFPP)PhIO。,PhIO,μ-,MnⅢ(TPFPP)Cl-PhIO,[26]。KHSO5O—O,NaOClm-CPBA。Mn(TMPyP)Fe(TDCPPS)carbamazepine(CBZ)[27]:CBZ99%,CBZ10,11-oxide80%75%。,Groves[28],(m-CPBA、KHSO5NaOCl)Mn(TMPyP),,MnⅤ(O),CBZ。P-450,,[26,29—32]。·387·5　　,,,,。,,,。Merlau[33]。(ZnTPPMnTPP),7。7　ZnTPP-MnDPyP-ZnTPP,(2-4)。,Sousa,,,,,MnP,MnPhIO,O[34]。、,,。,:;,。,,,,。,,。Co(TMP)Y[35],。[36]NaX,,。,。,。[37]3-MCM-41,[Ru(Ⅱ)L(CO)(EtOH)](L=meso-terakis(4-clorophenyl)porphyrin),6,,20—40,,。,Liu[38]MCM-41[RuⅡ(TDCPP)(CO)(EtOH)],2,6-,。,,,1。Zhan[39]“”MnTMAnP@NaY(MnTMAnP=trakis(N,N,N-trimethy-lanilinium)manganeseporphyrincations)(8),,,5。,VianaRosa[40]FeP1FeP2NaX(9),PhIO,(Z)-,85%95%。,·388·化　学　进　展141　MCM-41Ru(a)Yieldsarebasedontheamountofsubstratesconsumed;productswereidentifiedandquantifiedbyeitherGLCorHNMRusingtheinternalstandardmethodunlessotherwisestated.(b)Traceamountsofbenzaldehydeandphenylac-etaldehydewerealsodetected.(c)Traceamountofbenzaldehydewasdetected.(d)Isolatedyield.(e)2-Cyclohexen-1-ol(14%)and2-cyclohexen-1-one(11%)wereformed.(f)Glycal(0.5mmol),Cl2pyNO(0.62mmol),0.4wt%Ru/M-41(m)(0.195μmolofRu),HCl(～0.3mmol),CH2Cl2(5mL),40℃underanAratmosphere.(g)Overallisolatedyieldaftere-poxidationandmethanolysis;ratioofα∶β-epoxides=3∶1.(h)Turnoverfrequencies(TOF)weredeterminedbymonitoringthereactionsusingGCwithinthefirst2hofthereactions.nd:notdetermined.8　NaYMnTMAnP。,,,,,。、,P-450,。,,,,。,,,,。·389·5　　9　NaX(Ⅰ)(FeP)[1]CollmanJP,WagenknechtPS,HutchisonJE.Angew.Chem.Int.Ed.Engl.,1994,33:1537—1554[2]RodgersKR,ArafaIM,GoffHM.J.Chem.Soc.,Chem.Commun.,1990,1323—1324[3]MennierB.Chem.Rev.,1992,92:1411—1456[4]McLainJ,LeeJ,GrovesJT.inBiomimeticOxidationsCatalyzedbyTransitionMetalComplexes(edMeunierB).London:InperialCollegePress,2000.91—196[5]SonoM,RoachMP,CoulterED,etal.Chem.Rev.,1996,96:2841—2887[6]MachiiK,WatanabeY,MorishimaI.J.Am.Chem.Soc.,1995,117:6691—6697[7]TraylorTG,KimC,FannWP,etal.Tetrahedron,1998,54:7977—7986[8]TraylorTG,KimC,RichardsJL,etal.J.Am.Chem.Soc.,1995,117:3468—3474[9]BruiceTC.Acc.Chem.Res.,1991,24:243—249[10]HeGX,BruiceTC.J.Am.Chem.Soc.,1991,113:2747—2753[11]AlmarssonO,BruiceTC.J.Am.Chem.Soc.,1995,117:4533—4544[12]TraylorTG,TsuchiyaS,ByunYS,etal.J.Am.Chem.Soc.,1993,115:2775—2781[13]WatanabeY,YamaguchiK,MorishimaI,etal.Inorg.Chem.,1991,30:2581—2582[14]PrattJM,RiddTL,KingLJ.J.Chem.Soc.,Chem.Commun.,1995,2297—2298[15]KamarajK,BandyopadhyayD.J.Am.Chem.Soc.,1997,119:8099—8100[16]ToyPH,NewcombM,CoonMJ,etal.J.Am.Chem.Soc.,1998,120:9718—9719[17]PrimusJL,BoersmaMG,MandonD,etal.J.Biol.In-org.Chem.,1999,4:274—283[18]NewcombM,ShenR,ChoiSY,etal.J.Am.Chem.Soc.,2000,122:2677—2686[19]LeeYL,GohYM,