糖合成中羟基的保护和去保护方法

163Vo.l16No.320059CHEMICALRESEARCHSep.2005:2005-05-07.:(1980-),,..Emai:[e-mail].李鹏飞1,吉毅1,颜杰2,李宗石1,乔卫红1(1,116012;2,643000):..:.,.:;;;:O629.1:A:1008-1011(2005)03-0107-06ProtectionandDeprotectionofHydroxylGrouponCarbohydratesLIPengfei1,JIYi1,YANJie2,LIZongshi1,QIAOWeihong1(1StateKeyLaboratoryofFineChemicals,DalianUniversityofTechnology,Dalian116012,Liaoning,China;2DepartmentofChemistry,SichuanUniversityofScience&Engineering,Zigong643000,Sichuan,China)Abstract:Therearemanyactivehydroxylgroupsoncarbohydrates.Theprotectionanddeprotectionofhydroxylgroupsareimportanttothesynthesiswithcarbohydrates.Thehydroxylgroupscanbechangedintoesters,ethers,acetalsandketals,etc.Thispaperreviewsthecharacteristicsandutilitiesofprotectivegroups.Themethodsofprotectionanddeprotectionofhydroxylgroupsoncarbohydratesareintroducedespecially.Keywords:carbohydrate;hydroxylgroup;protection;deprotection,,,.:.,..11.1.()[1][2].,.,.2,3,4,3,4C4C6,2,3,6,3,4[3]..,[4],NH3/MeOH(NaOMe/MeOH).[5],.10820051.2,.:////.D5,6D[6]:.Wright[7]D1,:Br2Pb(OAc)4HBr/AcOHH2Pd,,.1.3()..,,C3.D,C6C2,D,C2C6C3C6[8]:Bu4NOH20.1.4UCP(unichemoprotection),Komba[9]-UCP().UCP,EdmanUCP,.,.3:109:()monoUCP,,,40,2h,90%.()80%,60,2h,79%.()triUCP,,40,2h,65%.(),,40,2h,91%.()a:20%N,N,,20min.b:EdmanPITC,N,,30min.c:,,,30min.d:Boc2O,,N,N,,30min,69%.22.1.,DMF,Ag2O,,[10].[11],,,.[12].Bu2SnO,:[13],,,,:,,.,.,,.2.2(trityl),,,.[3][14].(MMT)(DMT).SN1,:DMTMMTTrity.l,.80%()/()/,,.Lehrfeld[15],80%,.11020052.32.3.1三甲基硅醚类,[16].,,[17].,,,[18]:(/THF)./.2.3.2叔丁基二甲硅醚(tBuMe2Si简称TBDMS)TBDMS,.,DMFTBDMS[19].TBDMSOTf,C3C6C2C6[20].,(Zn/CH3OH).(Bu4N+F-).(66%).2.4,,.[21]Williamson.,,.,C4C6:,,:(DMSO),.1molL-10.5molL-1,,:,HgCl2,,..,,:33.1(,,,),,.2,22,2,3:111,[22].[23],,.46,,,DZnCl2/H3PO41,2:5,6D[24].,.FeCl3/SiO2,5612[25]:3.2(,,),C4C6.[26],,,,.,,,.Sheman[27]PhCH(OMe)2,(CSA)DMFC4C6,85%..(Pd/C);Sheman[27]Me3NBH3AlCl3THF,46.FeCl3/SiO24,6[25]:4,,,,.,.Wong[28],2346;Castoldi[29]2326.,.:[1]褚吉成,郭洪声,王松青.1,2O3,4O[J].,2004,37(5):434-437.[2]刘振东.D[J].(),2001,21(2):17-20.[3]郑建仙,李璇,袁尔东.[J].,2002,28(2):1-6.[4]MakiT,IchiroM,YukishigeI.Pentafluoropropionylandtrifluoroacetylgroupsfortemporaryhydroxylgroupprotectioninoligomannosidesynthesis[J].CarbohydrRes,2003,338:1073-1081.[5]李雯,刘宏民,尤启冬.[J].,2003,61(9):1516-1520.[6]OverendWG,StaceyM,WigginsLF.Deoxysugars.PartAsynthesisof2deoxyDribosefromDerythrose[J].JChemSoc,1949,3:1358-1363.[7]TenerGM,WrightRS,KhoranaHG.AsynthesisofDribofuranose1phosphate[J].JAmChemSoc,1956,78(2):506-507.[8]LuJ,ChanTH.Regioselectiveacylationofhexopyranosideswithpivaloylchloride[J].JOrgChem,1998,63:6035-6038.1122005[9]ShiroK,MotomitsuK,TakafumiK,etal.Anewoligosaccharidesynthesisusingspecialhydroxylprotectinggroup[J].TetrahedronLett,2004,45:2759-2762.[10]DeredasD,FrankowskiA.SynthesisofDerythrofuranosylCnucleosidesofimidazolefrom4(5)(Darabinotetritol1yl)imidazole[J].CarbohydrRes,1994,252:275-281.[11]MichelB,JilaS,KostasA.CrownethercatalyzedOalkylationofcarbohydratesandnucleosides[J].Synthesis,1988,560-562.[12]NashedMA.AnimprovemethodforselectivesubstitutiononO3ofDmannose.ApplicationtothesynthesisofmethylO3methyland2OmethylDmannopyranosides[J].CarbohydrRes,1978,60:200-205.[13]董奇志,郭振楚,谭凤娇.O[J].,2001,9(6):560-562.[14]巨长丽,方志杰,许金峰.D[J].,2003,33(5):41-42.[15]JacobL.Silicagelcatalyzeddetritylationofsomecarbohydratederivatives[J].JOrgChem,1967,32(8):2544-2546.[16]SweeleyCC,BentleyR,MakitaM,etal.Gasliquidchromatogramphyoftrimethylsilylderivativesofsugarsandrelatedsubstances[J].JAmChemSoc,1963,85(16):2497-2507.[17]LichtenthalerFW,KohlerB.Anexpedientroutetoacylatedglucosylhalideswithafree2OHgroup[J].CarbohydrRes,1994,258:77-85.[18]McinnesAG.ThealcoholysisoftrialkylalkoxysilanesPart.Akineticstudyofthemethanolysisofmethyl2,3,4,6tetraOtrimethylsilylDglucopyranosidetoformmethyl2,3,4triOtrimethylsilylDglucopyranoside[J].CanJChem,1965,43:1998-2003.[19]CoreyEJ,VenkateswarluA.Protectionofhydroxylgroupsastertbutyldimethylsilylderivatives[J].JAmChemSoc,1972,94(17):6190-6191.[20]IkedaY,FurukawaK,YamadaH.Simultaneousregionselectiveprotectionofphenyl1thioglucosidesattheC3andC6orattheC2andC6hydroxylgroups[J].CarbohydrRes,2002,337:1499-1501.[21]刘煜,卢志云,邢孔强,等.[J].,2001,13(1):39-45.[22]GelasJ,HortonD.KineticacetonationofDgalactose,Dallose,andDtalosewithalkylisopropenylethersasapreparativeroutetothe4,6isopropylidenealdohexopyranoses[J].CarbohydrRes,1979,71:103-111.[23]甘中红,孔繁祚,汪勤慰.TiCl4[J].,1996,15(2):179-182.[24]张卫红,冯亚青,刘云华,等.1,2D[J]..2005,22(2):92-95.[25]KimKS,SongYH,LeeBH,etal.Efficientandselectivecleavageofacetalsandketalsusingferricchlorideadsorbedonsilicagel[J].JOrgChem,1986,51:404-407.[26]蒋爱琴,方志杰,赵成芳,等.4,6[J].,2000,22(4):203-204.[27]ShermanAA,YudinaON,MironovYV,etal.StudyofglycosylationwithNtrichloroacetylDglucosaminederivativesinthesynthesisofthespacearmedpentasaccharidessialyllactoNneotetraoseandsialyllactoNtetraose,theirfragments,andanalogues[J].CarbohydrRes,2001,336:13-46.[28]WongCH,YeXS,ZhangZY.Assemblyofoligosaccharidelibrarieswithadesignedbuildingblockandanefficientorthogonalprotectiondeprotectionstrategy[J].JAmChemSo