非膦配體參與的鈀催化有機反應研究.pdf

1、中國科學技術大學博士學位論文非膦配體參與的鈀催化有機反應研究姓名：崔歆申請學位級別：博士專業(yè)：有機化學指導教師：郭慶祥20080401ABSTRACTPd—catalyzedCCbondformationreactionssuchastheHeckandSuzukicrosscoupllngsareplaylngmcreasinglymoreimportantr0】esinmodemo曜anjcs”t11esisJtlesecrossc

2、ouplingreactionsareusuallyperfomedwith15moi％ofPdcatalvstaIongwithphosphineligands，whichsometimescreatespracticalproblemsbecauseo曙anophospllincstendtobecxpellsiVc，poisonous，andairscnsitiveAccordingIv，anlmportantcurrentcha

3、llengeistodeVelopPdcatalyststhatcanutilizejnexDensivephosphine行ee】igands1ntnlspape。wereportseVeralnoVelandef佗ctiVephosphinefreePdcatalvticsystemsⅣ，Ⅳdimethyl一p。alaninewasfoundtobeamorepowerfulphosphjncrree119andthanthepre

4、Viouslyrcponed】igand，MⅣ_dimeIhylgIycinc，inthePd。cacalyzedHeck托actionandSuzukireactionforaVarietyofaryIbromides，aryliodides，andactiVatedarylchlorjdeswithapracticaItumovelnumberof103Bothkineticandthe9retlcaIstudlcssuggeste

5、dthatⅣ，Ⅳdimethyl—p—alanjneledtofasteroxidaliveadditionofanarylhalidetoPdthanⅣ，，dinlcIhylglycinepunhermore，wehaVes”thesizedanoVeIcrystalJine，air—stable，andmoisture。stablePdsalt，Pd(Ⅳ，Ⅳdimethyl—p—alaninate)2Thissaltwasdemon

6、stratedtoconstitutealow’prlced，phosp】1inefree，yethigh—turnoVer—numbercatalystfortheSuzukjrcactlonsofVarlousarylbromidesandiodidesundermiIdandsimpIereactjoncondltlonsweobserVedthatthepresenceofan01e打ncouIddramaticaJIyhanl

7、pertheSuzukireactionrfothebestofourknowledge，thisnewnndingprovidedinterestin2mecnanlstlclnslghtsIntothelowerreactiVityo九heIcckreactionascomDare(1totheSuzukireactjnn』)v。phenylureawasfoundtoconstituteahi曲Iyemcient，yetlowpr

8、iced，p110sphinc_行eeIigandforthePd—catalyzedHeckandroomtemperatureSuzuki。eac‘ionsofarylbromidesandiodideswithVeryhighturnovernumbers(c以103—104)ItisalsofoundthatⅣphenylureacanbeanexce】lent】igandinLarockindolizationof2bromo