d-生物素的不對稱全合成和相關反應的研究.pdf

1、復旦大學碩士學位論文d生物素的不對稱全合成和相關反應的研究姓名：彭作中申請學位級別：碩士專業(yè)：有機化學指導教師：陳芬兒2000.6.1復旦大學碩士論文AbstractdBiotinhasbeenwidelyusednotonlyasapharmaceuticaldrugbutalsoasalladditiveincosmeticsandfeedForthisreason，considerableeffoashavebeenmadefor

2、itstotalsynthesis，particularlythecommercialsynthesissinceitsisolationfrombeefliverin1941WimthegrowingdemandinititisimportanttodeveloparteffectiverouteforthesynthesisofdbiotintofillinthegapsinitsmanufactureofourcountryCha

3、pterlhasreviewedthetotalsyntheticmethodsofdbiotinsince1949，andanalyzedeachroutereportedinliteraturefromstandpointofindustrialproducingAtpresenttheStembach’Srouteisthemostconvenientapproach，butstillhavesomeshortcomingsThe

4、rearemanyimprovingstudiestodevelopittocommerciallevelinChinaInChapter2，anewrouteiSreportedfortheproductionofdbiotintakingadvantageoftheasymmetrysynthesisandthenovelstrategy(c6一ci=c5)introducingsidechainattheC4positionin(

5、3aS6aR)一5Thekeyintermediate(3aS6aR)一l，3一dibenzyl—tetrahydro4Hthieno[3，4d】imidazol2，4(1加一dione(5)isobtainedwithveryhighenantiostereoselectivityandingoodchemicalyieldviacondensmionof13一dibenzylimidazolidone2一c插一4，5dicarbox

6、ylicacid(10)asstartingmaterialwithopticalactiveprimaryaminesaschiralauxiliarydiastereoselectivereduction，hydrolysis／cyclizationandsulfurationTheC6sidechain6ispreparedinthreestepsstartingfroml—bromo一3一chloropropaneandethy

7、lacetoacetateTheintroductionofC6sidechainattheC4positioninf3aS6aR)一5isaccomplishedefficientlybyutilizingtheGrignardreactionof(3aS6aR)一5with6ThetransformationofaseriesoffunctionalgroupsinC4positionsidechainiscarriedouttoa

8、frorddbiotinviastereospecifichydrogenationandhaloformreactionT11istotalsyntheticapproachwith25％overallyieldofdbiotininsevenstepsbasedon10hastheadvantagesofmildreactionconditionsandinexpensiverawmaterialswhichmakeitsappli

9、cationinindustryhopefulTheformationofthemajorbyproductsisexplainedTheprocessof9—爭8andthepossiblemechanismof14—13arealsodescribedThestructuresofallcompoundssynthesizedarecharacterizedbyIR，1HNMRandMSTheconfigurationsof(4S5