輔酶NADH模型物還原反應立體專一性研究.pdf

1、中國科學技術大學博士學位論文輔酶NADH模型物還原反應立體專一性研究姓名：李勁申請學位級別：博士專業(yè)：有機化學指導教師：劉有成鄧金根1999.12.1AbstractCoenzymeNADHplaysavitalroleinbiologicaloxidationandreductionreactionsItcanreducemanyprochiralcarbonylcompoundsandotherunstaturatedcompoun

2、dswithhighenantioselectivityThestereochemistryandreactionmechanismofthereductionwithNADHmimicshavebeenallinterestingtopicinthefieldofphysicalorganicchemistryandbiologicalchemistryCyclopropanecompoundsareimportantreaction

3、intermediatesoforganicsysthesisandcyclopropanesubunitsarefoundinmanynaturalorunnaturalproductsClairalcyclopropanecompoundsareofgreatvalueinasymmetricorganicsysthesisThethesisWOrkiSconcemedwiththestudyofasymmetriccyclopro

4、panationreactionsof(Ss)l—benzyl3(ptolylsulfinyl)一14dihydropyridinewith2bromo一1phenylethylidenemalononitrileFirstofall，animprovedsyntheticprocedureofchiralNADHmodel(Ss)1一benzyl3Co—tolylsulfinyl)1，4一dihydropyridinehasbeenw

5、orkedoutTheoveratchemicalyieldoftheimprovedprocedureisverystableandrepeatabilityisverygoodFurthermore，theopticalrotationof(Ss)一1benzyl一3一(p—tolylsulfinyl)一1，4一dihydropyridineishigherthanthatreportedintheliteratureThrough

6、experimentsonthecyclopropanationreactionsofthischiralNADHmodeiwith2bromo一1phenylethylidenemalononitrileundervariousreactionconditions，itWasfoundthattheenantioselectivitiesofthereactionsweremoderate(upto560％ee)Thereaction

7、ratesincreasedwiththeincreaseofsolventpolarityandtheenantioselectivitiesofthereactionsbecamelowerwiththeincreaseofreactiontimenleresultsareexplainedbytheringopenningringclosureequilibriuminthepresenceofbromideionFromther

8、esearchofcyclopropanationreactionsofthischiralNADHmodelandothersubstrateswithsimilarstructure，itWasfoundthatthesubstituentgroupattheDpositionoropositionofphenylgroupofsubstratecouldaffectthereactionenantioselectivitiesre

9、markablyItwasthesizeofthesubstituentgroupratherthantheelectronwithdrawingabilitythatshowedtheeffectNoproductwasobtainedinthereactionofsomeO—substitutedsubstrateOntheotherhand、thechangingofsubstituentgroupatmethylenegroup