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《新型二茂鐵類手性膦-亞磺酰胺配體的合成及其在不對稱催化反應(yīng)中的應(yīng)用》由會員上傳分享，免費在線閱讀，更多相關(guān)內(nèi)容在學(xué)術(shù)論文-天天文庫。
1、第四軍醫(yī)大學(xué)碩士學(xué)位論文Anewtypeofferrocene-basedphosphine-tert-butylsulfinamideligands:synthesisandapplicationinasymmetriccatalysisCandidateformaster:MaJiangweiSupervisor:ProfessorJiangRuDepartmentofMedicinalChemistry,Schoolofpharmacy,FourthMilitaryMedicalUniversity
2、,Xi’an710032,ChinaSponsoredPrograms:NaturalScienceFoundationofChina(21272271,21472240)AbstractThephosphineandsulfonamidegroupareintroducedinferroceneskeletonwhichisthechiralligandadvantageframework.Therefore,thesevennovelferrocene-basedphosphine-tert-buty
3、lsulfinamideligands(L1-L7)weredesignedandsynthesized,whichcontainplanarchiral,carbonchiral,sulfurchiralandotherchiralfactors.AndtheyareappliedinthePalladium-catalyzedasymmetricallylicsubstitutionreactionsandRhodium-catalyzedasymmetricarylationfortestingth
4、eircatalyticactivityandenantioselectivity.Themaincontentsareasfollowed:1.Thesevennovelferrocene-basedphosphine-tert-butylsulfinamideligandsweredesignedandsynthesizedfromUig’samineastheoriginalmaterial.Afterfourstepsofreactions,thetargetligandsareobtaineda
5、ndconfirmedtheirstructureswithNMRandHRMS.2.Thechiralligands(L1-L7)werefirstlyappliedinthePalladium-catalyzedasymmetricallylicsubstitutionreactions.Theresultsindicatedthatthechiralitiesofferrocenylmoietyintheligandsplaythedecisiveroleinthisreactions.Whilet
6、he-9-第四軍醫(yī)大學(xué)碩士學(xué)位論文carbon-centredchiralityandtheplanarchiralityofferrocenescaffoldarethemaingoverningfactors,thesulfur-centredchiralityofsulfinamidemoietyisalsoimportant,and(RC,SFc,RS)-L1aretheligandswiththematchedchiralities.Tofurtherimprovethechemicalyiel
7、dandenantioselectivity,weoptimizedthereactionconditions,suchastheproportionofcatalyst,solvent,temperature,additive,baseandPalladiumsourceandsoon.Intheoptimalcatalyticconditions,thepalladiumcomplexderivedfromligandL1wasanefficientcatalystinasymmetricallyli
8、calkylationofsymmetricaldisubstitutedlinearsubstrates(upto89%ee).Fortheasymmetricallylicamination,goodstereoselectivitieswerealsoobtained(upto87%ee).3.TofurtherstudythepotentialofligandL1,itwastesteditintheasymmetri
