無膦鈀催化heck反應(yīng)合成二苯烯型類維a酸

1、湖南大學(xué)碩士學(xué)位論文無膦鈀催化Heck反應(yīng)合成二苯烯型類維A酸姓名：劉西洋申請學(xué)位級別：碩士專業(yè)：有機化學(xué)指導(dǎo)教師：向建南20080520無膦鈀催化Heck反應(yīng)合成二苯烯型類維A酸IIIAbstractRetinoicacidisnonsteroidalsmallmoleculehmoneplaysakeyroleinthemaintenancedifferentiationofepithelialtissueisveryimptant

2、fthetreatmentofacneskindamagedbyUVlight.Furthermeithasbeenevaluatedftheirpossiblebeneficialeffectsinseveralcancerousconditions.Theactionsofretinoidsaremediatedthroughbindingactivationoftheretinoicacidrecepts(RARs)retinoi

3、dXrecepts(RXRs)whichfunctionasligdependenttranionfacts.Therefedevelopmentofreceptiveretinoidwhichhasastablestructurecausechemistsgreatinterest.Theaimofthisthesisistoresearchstructuraldesignsyntheticmethodsofnovelstilbene

4、receptiveretinoids.developmentofaefficientsynthesisftheimptantpharmaceuticalintermediatesSartanbiphenyl.Tworesultsobtainedweresummarizedasfollows:FirstaphosphanefreepalladiumcatalystconditionsftheHeckreactionusingdicyclo

5、hexylamineastheancillaryligswasinvestigatedestablishanewphosphanefreepalladiumcatalystHeckreactionsystem.Thissystemcanbehighyield（72%～84%）highstereoive（83%～95%）synthesisofthedisubstitutedtrisubstitutedstilbenecompounds.F

6、ournovelstilbenederivativesarotinoidmethylester(3a3b4a4b)weresynthesizedbyabovemethodusing245trimethoxystyreneαasaroneasstartingmaterial.Theirhydrolysatesarotinoicacid(5a5b6a6b)wereeasilyaccessibleundermildhydrolysiscond

7、itionsusingtheLiOHTHF:H2O=5:1system.Secondahighlyefficient2stepsynthesisoftheSartanbiphenyl(7)wasdeveloped68%oftotalyield.Themostimptantfeaturesarethefollowing:(1)usingMnCl2asacatalystfcrosscouplingreactionhaveavoidtheus

8、eofthepalladiumcatalystreducedthecostgreatly(2)inthepresenceofMnCl2Grignardreagentscaneasyreactwitharylchlideswhichhasanelectronwithdrawingactivatinggroup（CN，CH=NR，oxazoline），caneffectivelyprotectCNgroup(3)Thepossibleigi

9、nsofbyproductwerediscussedthereactionconditionwereoptimized(4)thepurifiedprocessoftheproductshasbeenimprovedwedescribeastepbystepcrystallizationofthepurificationprocess.Thisprocesstoavoidexpensivechromatographicpurificat