三甲基硅基作为保护基在有机反应中的应用

62()Vol.6,No.220004JOURNALOFSHANGHAIUNIVERSITY(NATURALSCIENCE)Apr.2000:100722861(2000)0120157208X,(,201800):,,.:;;;:O621.25:ATheApplicationofTrimethylsiylGroupasProtectiveGroupinOrganicSynthesisQUMing2hai,PUJia2qi(SchoolofSciences,ShanghaiUniversity,Shanghai201800,China)Abstract:Trimethylsiylgroupiswidelyusedintheprotectionoforganicfunctionalgroupsin2volvingheteroatoms,suchashydroxy,carboxylandaminogroup.Theconditionsofprotectionanddeprotectionandtheselectivityofthereagentsarediscussed.Keywords:silicareagent;protectivegroup;selectivity;organnicsynthesis70,,,,.1,.,,,.1.1.,(TMSCl),,[1].TMSCl[2,3],GrignardUll2mann..(HMDS),(TMSI)[4].,X:1999208226:(1973),,,,.,,[5,6].,C11C15mC9(),WittigCollins[7,8].TMSClLi2S[9],.R-OH+Me3SiCl+Li2SCH3CN25,12hR-OSiMe3+2LiCl+H2S,,,,,[10].R-OH+(Me3Si)2OTOSOHöC6H6$R-O-SiMe3+Me3SiOH,N,O2(),Grignard[11,12].N,O2()N,O2()[13],,,.Me3-NH-COOSiMe3+ROHTHFrapidROSiMe3+CO2+NH3Me3Si-NH-SO2-OSiMe3+2ROHCH2Cl20.5h2ROSiMe3+NH2-SO2-OH[14,15],851()6.[16][6,17][9,18],[7],L2HMDSöTMSCl,.()(BSA)()(BSU),,,[1921].102DeacetylbaccatinË(102DAB)102,N,O2(),THF05h,91%102TMS2102DAB[22].1.2,THF,9512,:[23].,B2,[24].,,CH3OHöK2CO3,[25].,,,ö[6],CH3OHöH2OöCH3CO2H[5].,,,23A225A223B2,HMDS,MontmorilloniteK210(K210),CH2Cl2[26].ROHK210,HMDS,r.t.,0.58h,098%K210,MeOH,r.t.,0.14h,8998%ROSiMe3,,[27a],[27b],,,.,BF32Et2OTMS[28].Na2S,TMS[29].K2CO3,TMS,tBuMe2Si2(TBDMS)[30].,LewisTMS[31],,Cu(NO3)2Ce(NO3)3,TMS[31].nC10H21OTMSCu(NO3)21minnC10H21OH(100%).2,,,,..Wittig[32]Ullmann[3].,CH2Cl2TMSCl[33].R-COOHTMSClöTMSICH2Cl2,30,2hR-COOSiMe3,72(72ACA)32,72ACA,[34],HMDS061()6,TMSI,CH2Cl2710h.Me3SiNHSO2SiMe3[12],,.CCl4,CH3CONHSiMe3,1h[35].Me3S-NH-SO2-OSiMe3+2R-COOHCH2Cl22R-COOSiMe3+NH2-SO2-OH,BSA[36],,,[37,38].3Si-N,,[3,39].Grignard[4042],.TMSClöEt3N[43],.,(CF3SO3SiMe3)[44],,,,,.,BSABSU[45,46],,,[47].Vorbrueggen,HMDSö(NH4)2SO4,,,TMS,[48].,,..1612,::[1]KkbeJF.Silylationswithbis(trimethylsilyl)ac2etamide,ahighlyreactivesilyldonor[J].JAmChemSoc,1966,83:3390.[2]MoreauC,RouessaxF.Thermocyclizationofalkenylphenols[J].TetrahedronLett,1970.3257.[3]KingFD,WaltonDRM.Protectionofaminoandhydroxygroupintheullmannreactionandrelatedorganocoppercoupling[J].Synthesis,1976,40.[4]MasatakaIhara,etal.ConstructionofpolycyclicringSystemsfusedtocyclobutanebycascadereactionsofformylA2B2unsaturatedEsters[J].Synthesis,1995,11:1405.[5]CooperEL,YankeeEW.Enantiomericprostaglandins[J].JAmChemSoc,1974,96:5876.[6]BundyGL,PetersonDC.Thesynthesisof152De2oxy29,112(epoxyimino)prostaglandinsprotentthrom2boxanesynthtaseinhibitors[J].TetrahedronLett,1978,41.[7]YankeeEW,BundyGL,AxenUA.Totalsynthesisof152methylprostaglandins[J].JAmChemSoc,1974,96:5865.[8]YankeeEW,BundyGL.(15S)2152methyl2prostaglandins[J].JAmChemSoc,1972,94:3651.[9]OlahGA,GuptaBGB.Chlorotrimethylsilaneandtert2butyldimethylsilylchlorideölithiumsulfide,mildandefficientsilylatingreagents[J].JOrgChem,1979,44:4272.[10]BalBS,LajisNH.Anewpreparationoftrimethylsilylethers[J].TetrahedronLett,1978.4261.[11]HornDHS,MiddletonEJ.Isolationofcustecdysone(20R2hydroxyecdysone)fromacray2fish[J].JChemSocCommun,1968.466.[12]CopperBE,WestallSG.NewsilylatingagentsItrimethylsilyltrimethylsilylamidosulphonate[J].JOrganometalChem,1976,118:135.[13]BirkoferL,SommerP.Alkyloxy2andsilyloxy2derivativesofPVandSbV[J].JOrganometalChem,1975,99:101.[14]VeysogluT,MitscherLA.AclassofnewsilylatingreagentsÊ[J].TetrahedronLett,1981,22:1302.[15]VeysogluT,MitscherLA.AclassofnewsilylatingreagentsÉ[J].TetrahedronLett,1981,22:1299.[16]WeiszL,FelfodiK,KovacsK.CA.SelectiveetherificationÉstereospecificformationoftrimethylsilylethersofsomesteroidsandtropanederivatives[J].1969,70:47668.[17](a)SweeleyCC,BentleyR,MakitaM,etal.Gas2liquidchromatographyoftrimethylsilylderivativesofsugarsandrelatedsubstances[J].JAmChemSoc,1963,8:2497.(b)FisherJC,NortonD.Stereospecificsynthesisofchiralbenzyliccentersfromd2erythro2pentulosederivatives[J].CarbohydrRes,1977,59:459.[18]VorbrvggenH,KrolikiewiczLiebigs.NucleosidesynthesisXXIsynthesisof52methylaminomethyl222thiouridine,ararenucleosidefromtRNA[J].AnnChem,1980.1438.[19]OhnoM,MastuokaS.Catalyticelectrophilicreac2tionsofchrysanthemicacidderivativeswithunsatu2ratedorganosilanes[J].JOrgChem,1986,51:4553.261()6[20]JacksonWP.Asimplepreparationofbis(trimethylsilyl)peroxide[J].SynthesisLett,1990.536.[21](a)YoungSD,BuseCT,HeathcockCH.(2S,3R)22,42dimethyl232hydroxypentanoicacid[J].OrgSynth,1990,381.(b)BalB,BuseCT,SmithK.22methyl222(trimethylsiloxy)pentan232one[J].OrgSynth,1990,185.[22]RobertAHolton,ZhangZhuming,ClarkePaulA.SelectiveprotectionoftheC(7)andC(10)hydroxylgroupin102deacetylBaccatinË[J].TetrahedronLett,1998,39(19):28832886.[23]MurofushiT,ShimizuM,KuwajimaI.Trimethylsi2lylacetate:anewclassofsilylatingreagentforke2tonesandalcohols[J].JAmChemSoc,1976,98:2346.[24]ChenSL,GrudzinskasCV.Prostaglandinsandcongeners27[J].JOrgChem,1980,45:2278.[25]McinnesAG.Thealcoholysisoftrialky2lalkoxysilanes[J].CanJChem,1965,43:1998.[26]ZhangZhanhui,LiTongshuang,YangFeng.Mont2morilloniteclaycatalysisÓ[J].SynCommun,1998,28(16):31053114.[27](a),.[J].,1999,19:34.