手性希夫碱的合成及其催化不对称硅氢插入反应的研究  

The Synthesis of Chiral Schiff Base and its Application in the Catalysis of Asymmetric Si—H Insert Reaction

作　　者：杨伟[1] 杨科芳[1] 郑战江[1] 徐利文[1] 

机构地区：[1]杭州师范大学有机硅化学及材料技术教育部重点实验室,浙江杭州311121

出　　处：《杭州师范大学学报（自然科学版）》2013年第6期486-490,527,共6页Journal of Hangzhou Normal University(Natural Science Edition)

基　　金：国家自然科学基金项目(21173064;51203037)

摘　　要：合成了结构中同时含有氮和磷的新型手性希夫碱,将希夫碱与金属配合物结合催化α-苯基-α-重氮乙酸甲酯与硅氢化合物的不对称硅氢插入反应,考察了不同的金属铜配合物和希夫碱对反应的影响,探讨了手性希夫碱/金属配合物催化体系对不同硅氢底物的适应性.当采用希夫碱4与Cu(CH3CN)4PF6的催化体系催化α-苯基-α-重氮乙酸甲酯与二甲基苯基硅烷的不对称硅氢插入反应时,反应具有优良的产率(100%)和对映选择性(76%).New chiral Schiff base containing nitrogen and phosphorus was successfully synthesized. The chiral Schiff base cooperated with different metal complexes were used to catalyze the asymmetric Si-H insert reaction of α-phenyl-α- methyl diazoacetate and the compounds containing Si-H groups. The paper investigated the effects of the copper complexes and the Schiff base on the reaction, and discussed the suitability of this catalytic system on the substrates containing Si-H groups. When using the Schiff base 4/Cu（CH3CN）4PF6 to catalyze the asymmetric Si--H insert reaction of α-phenyl-α- methyl diazoacetate and dimethyphenylsilane, the reaction had excellent yield（100%） and good enantioselectivity（76 %）.

关 键 词：手性希夫碱 硅氢插入 不对称 催化 

分 类 号：O626.5[理学—有机化学]