非膦配體參與的鈀催化有機(jī)反應(yīng)研究.pdf

1、中國科學(xué)技術(shù)大學(xué)博士學(xué)位論文非膦配體參與的鈀催化有機(jī)反應(yīng)研究姓名：崔歆申請(qǐng)學(xué)位級(jí)別：博士專業(yè)：有機(jī)化學(xué)指導(dǎo)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