84手性酮催化的烯烃不对称环氧化反应

©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(a071001)(b071001),.,.,,,AsymmetricEpoxidationofOlefinsCatalyzedbyChiralKetonesWANG,ChunX,aWU,Qiu2HuabYANG,Li2HuaaTANG,Ran2XiaoaYANG,Xu2ZheaGUO,Xiu2MinaFENG,Shuoa,bLI,Gui2Shena(aCollegeofScience,AgriculturalUniversityofHebei,Baoding071001)(bKeyLaboratoryofBioinorganicChemistry,AgriculturalUniversityofHebei,Baoding071001)AbstractChiralketoneisapowerfulcatalystforasymmetricepoxidationofunfunctionalizedolefins.Dioxiranes,whichcouldbegeneratedinsitufromchiralketoneandpotassiumperoxomonosulfate(Oxone),areremarkablyeffectiveoxidationreagentsforasymmetricepoxidationofolefins.Theapplicationofavarietyofchiralketonesinenantioselectiveepoxidationoftrans2olefins,trisubstitutedolefinsandcis2olefinsisreviewed.Thecatalyticactivityandtheasymmetricinductioninfluencedbythestructureofchiralketoneandthereactionconditionsarealsodiscussed.Keywordschiralketone,asymmetricepoxidation,unfunctionalizedolefin,dioxifane,,[13],,.,1980Sharpless[4]-,.1990Jacobsen[5]Katsuki[6]salen2,,,.,-,[7].,,,,,.1984Cusci[8],,.,,,.,XE2mail:[e-mail]25,2003;revisedAugust26,2003;acceptedSeptember4,2003.©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(KHSO5,:OxoneTM),KHSO5,,.11984Cusci[8]12Oxone,,.(9%12.5%ee),:1998Yang[9](R)23,(X).,,.3b,3b(S,S)2,72%89%ee.,3bee85%,,3b4ee32%.2000Solladie2Cavallo[10]25,,(2%40%ee).2C21996Yang[11]C26aKHSO5,,(33%87%ee),(5%18%ee).3,36,Yang[12]6b6h,,,ies(Entries14,58),6b,6c,6g.KHSO5,6,-2NaHCO3(pH=77.5),10mol%,6,21,221[12].1621,22Table1Asymmertricepoxidationoftrans2stilbenecatalyzedbyketone6EntryKetoneTime/hYield/%ee/%Config.1(R)26a19147S,S2(R)26b29576S,S3(R)26c39275S,S4(R)26d229032S,S5(S)26e19356R,R6(R)26f1.89260S,S7(R)26g0.79571S,S8(S)26h2044R,R(DME)--,0,.2[12].,(R)26g,7a7eee84%95%,.183No.4:©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(R)26ba,b(R)26ca,b(R)26ga,c(R)26gd7aH767571847bMe808584887cEt858882917di2Pr859088917et2Bu91939095a,6KHSO57=0.151,CH3CN2H2O2NaHCO3;b23h;c40min;d0,20h,6KHSO57=0.1101,DME2H2O2NaHCO3.,DME2-,ee,6[13].6,.,6,,.C289,.,21,22,894%50%ee[13];980%88%ee[14].31996,,ShiD210[15],(70%95%ee),.Yang,-,NaHCO3pH78,()Baeyer2Villiger,310.:,pH,K2CO3NaHCO3,pH(pH10),()Baeyer2Villiger,[16],10%,.,.().12%56%[17].3.310Table3Asymmertricepoxidationofolefinscatalyzedbyketone10SubstrateSolventYielda/%eea/%Config.CH3CN2H2O9391.7(+)2R,RCH3CN2H2O7597(+)2R,RCH3CN2H2O7090(+)2R,RCH3CN2H2O8794(+)2R,R283Vol.24,2004©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(+)22S,3RCH3CN2DMM2H2O5594(+)2R,RCH3CN2H2O7091(+)2R,RCH3CN2H2O8893(+)2R,RCH3CN2H2O6693.5(+)2RCH3CN2DMM2H2O9193.3(+)2R,RCH3CN2DMM2H2O7895.7(2)2R,Ra0,10KHSO5Substrate=0.31.381.10,,89%97%,[18].,,,.10,ee[19].10.L210,[17,18,20].D2,11,,90%[21,22].KHSO5,D2,[2326].N212,4[23].412Table4Asymmertricepoxidationofolefinscatalyzedbyketone12SubstrateKetoneYield/%ee/%Confign12a71832R,3S12b60842R,3S12c72902R,3S12d55902R,3S12e59782R,3S12a12b56608080R80R383No.4:©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(-)21314,14,,10mol%,[27,28].14,5.514Table5Asymmertricepoxidationofolefinscatalyzedbyketone14EntryRYielda/%ee/%Config.14aH1193R14bCH2OTBS7790R14cCH2OAc9590R14dCH2OCOAc9190R14eCH2F7189R14fCMe2OH9196R14gCMe2OMe9496R14hCO2Me6695RaKetoneKHSO5Sub.=0.11.381,-10,6h,DME2DMM2H2O2K2CO3..14c1,3222280%,94%ee.(52%67%ee),14c67%ee.(-)2(13)15,1617,(50%).1588%89%ee[29].5Armstrong[30,31]18,19,-,20124h,1020mol%,6.618,19-Table6Asymmertricepoxidationoftrans2stilbenecatalyzedbyketone18and19KetoneKetoneOxoneSub.Time/hYield/%ee/%18a1100103887618b150531006619a150511006319b150524852462023(9%40%),(85%100%),:21,012h,ee35%,85%[32,33].483Vol.24,2004©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(inChinese).(,,,,,,,2000,p.159.)2Bonini,C.;Righi,G.Synthesis1994,225.3Xiong,Z.;Corey,E.J.J.Am.Chem.Soc.2000,122,4831.4Katsuki,T.;Sharpless,K.B.J.Am.Chem.Soc.1980,102,5974.5Zhang,W.;Leobach,J.L.;Wilson,S.R.;Jacobsen,E.N.J.Am.Chem.Soc.1990,112,2801.6Irie,R.;Noda,K.;Ito,Y.;Katsuki,K.TetrahedronLett.1990,31,7345.7Groves,J.T.;Viski,P.J.Org.Chem.1990,55,3628.8Curci,R.;Fiorentino,M.;Serio,M.R.J.Chem.Soc.,Chem.Commun.1984,155.9Yang,D.;Yip,Y.2C.;Chen,J.;Cheung,K.2K.J.Am.Chem.Soc.1998,120,7659.10Solladie2Cavallo,A.;Bouerat,L.Org.Lett.2000,2,3521.11Yang,D.;Yip,Y.2C.;Tang,M.2W.;Wong,M.2K.;Zheng,J.2H.;Cheung,K.2K.J.Am.Chem.Soc.1996,118,491.12Yang,D.;Wang,X.2C.;Wong,M.2K.;Yip,Y.2C.;Tang,M.2