磺酰胺基醇的合成及其在炔基锌对醛和酮对映选择性加成反应中的应用

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1、兰州大学博士学位论文磺酰胺基醇的合成及其在炔基锌对醛和酮对映选择性加成反应中的应用姓名：倪明申请学位级别：博士专业：生物化学与分子生物学指导教师：王锐20060601◎躲慧AbstractCatalyticasymmetricreactionsareamongthemostimportantorganicreactions，whichcreategoodfortunestoenantiomericallypurechiraldrugsandothermaterials，andcontinuetobeoneofthemoststudiedandimportantareasinorga

2、nicchemistry．Opticallyactivepropargylalcoholsareimportantandversatilebuildingblocksforthesynthesisofawiderangeofpharmaceuticalsandnaturalproducts．Theenantioselectivealkynylzincadditiontocarbonylcompoundsisveryusefulforthesynthesisofchiralpropargylalcoholsandhasgainedconsiderablesignificanceinr

3、ecentyears．Hereinwemainlydiscussdesignandsynthesisofsomenovelchiralligandsorcatalystsandtheirapplicationtotheasymmetricadditionofalkynylzinctoaldehydesandketones．a)Fromc6mmerciallya'iailablenaturalL-phenylalanine，novelC2-symmetricalbissulfonamideligands56—57wereeasilypreparedinthreesimplesteps

4、andappliedintheenantioselectiveadditionofalkynylzincreagentstoaldehydes．Ligand56WaSfoundtobeanoutstandingligandforthisreaction，Hi豳enantioseleetivitywithaneevalueupto97％wasachievedunderverymildCOnditions．．b)Bythesameroutine，novelC2-symmetricalbissulfonamideligands56—57wereeasilyprepared，whichwe

5、reappliedintheenantioselectiveadditionofalkynytzinctoketonesinthepresenceofTi∞一i—Pr)4．Ligand56incombinationwithTi(O—·i--Pr)4wasfoundtobeeffectiveinpromotingtheadditionreactionofanalkynylzincreagenttounactivatedsimpleketonesunderverymildconditions．Thecorrespondingchiraltertiarypropargylicalcoho

6、lswereobtmnedwit}lenantiomericexcessesofupto81％．c)Startingfromnaturalaminoacides，weconvenientlypreparedligands60a—eandappliedthemintheenantioselectiveadditionofphenylacetylenetoketones。D—sulfonamidealcohol60bincombinationwithTi(O—i—Pr)4wasfoundtobeeffectiveinpromotingtheadditionreactionofanalk

7、ynylzincreagenttounactivatedsimpleketonesunderverymildconditions．Thecorresponding◎皑chiraltertiarypropargylicalcoholswereobtainedwi也enantiomericexcessesofupto80％。d)Startingfromnatural(+)一camphor,9-sulfonamidealcohol6Swasconvenientlyprepa