PDF论文在线浏览-聚合物负载手性BINOL催化剂的合

BINOL*3000711,1-chiralpocketchiralwall121,1-BINOLFig.11979NoyoriBINOL3BINOL()4,BINOLBINOL(SiO2)5OHOHOHOHFig.1thestructureofRorS2,2’-dihydroxy-1,1’-binaphthylOHOHB(OH)2Br+suzukireactionOHOH=polystyreneBINOLBINOL()BINOLSuzukiC-C66SuzukireactionBINOL,Fig.2BINOLFig.2synthesisofimmobilizedBINOLviaSuzukireactionHNMRFTIR(Fig.3;Fig.4)BINOLBINOL0.63mmol/g.Fig.3solid-stateHNMRofimmobilizedBINOL4000380036003400320030002800260024002200200018000102030405060708090100110ps-BINOLps3529.46TransmittanceWavenumberSPS-cat.(0.4equiv.),Solvent,H2OTBHP,0oC(2equiv.)SOFig.4FTIRspectrumofimmobilizedBINOLTi(Oi-Pr)4BINOL(1).1.ee80.1Tab.1effectofsolventonthecatalyticpropertyofimmobilizedBINOL1ee(/)98.1c/80.1a72b/57.3an.d./21a96b/17.9a2(/)32c/<20a46b/39an.d./41a28b/n.da.:TBHP:PS-BINOL:Ti(OPr-i)4:H2O=1:2:0.4:0.2:4,0,48b.[5]c.:TBHP:BINOL:Ti(OPr-i)4:H2O=1:2:0.4:0.2:4,0,24n.d.:notdetermined(2).ee()(Fig.5).0ti1020304050607080020406080(%)me(hours)concentrationofsulfoxideeevalueofsulfoxideFig.5eevaluesvsreactiontime(3)2eeICPTiBINOL123ee%57.348.854.9%39.045.035.0Tab.2recycledexperimentsforimmobilizedBINOL1NoyoriR.AsymmetricCatalysisinOrganicSynthesis;JohnWiley&Sons:NewYork,1994.2McCarthyM.;GuiryP.JTetrahedron2001,57,38093BrunelJ.MChem.Rev,2005,105,8574FanQ.H.,LiY.M.,ChanA.S.CChem.Rev,2002,102,33855.YangX.W.;ShengJ.H.;DaC.S.;WangH.S.;SuW.;WangR.;ChanA.S.CJ.Org.Chem.2000,65,2956.SuzukiAJ.OrganometallicChem.1999,576,147Thesynthesisofpolymer-immobilizedBINOLanditsapplicationinasymmetriccatalysisLiHaiyan,YuanXiaoyaZhangzhengpu*InstituteofPolymerChemistry,Tianjin,300071ChinaAbstract:Theimmobilizationof2,2’-dihydroxy-1,1’-binaphthyl(BINOL)ontopolystyrenemicrosphereviaSuzukireactionisdescribed.Theresultingimmobilized-BINOLwascharacterizedbysolid-state1HNMRandFTIRspectraandusedtocatalyzetheasymmetricoxidationofmethylphenylsulfide.Theeffectofsolventandreactiontimeonthecatalyticactivitywasalsodemonstrated.Itwasfoundthatsolventhadsignificantinfluenceontheactivityandenantioselectivity,tolueneandTHFwasthebestforthisheterogeneouscatalysiswitheeupto80.1%andtheimmobilized-BINOLcouldbeeasilyrecycledforatleastthreetimeswithoutlossofactivityandenantioselectivity.Keywords:heterogeneouscatalysis2,2’-dihydroxy-1,1’-binaphthylasymmetricoxidation