聚Salen-Ti(Ⅳ)配合物对芳香醛不对称硅腈化反应的催化作用  

Application of Polysalen-Ti(Ⅳ) Complex for Asymmetric Cyanosilylation of Benzaldehyde and Its Derivatives

作　　者：江万义[1] 姚小泉[1] 宋玉明[1] 胡信全[1] 陈惠麟[1] 白长敏[1] 郑卓[1] 

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023

出　　处：《催化学报》2003年第1期57-60,共4页

基　　金：国家自然科学基金重点资助项目 (2 99330 5 0 )

摘　　要：研究了聚SalenD Ti(Ⅳ )配合物对芳香醛不对称硅腈化反应的催化作用 .考察了催化剂用量、溶剂和温度对苯甲醛不对称硅腈化反应的影响 ,在 - 40℃和 1 0mol催化剂量下 ,以 4 Cl C6 H4 CHO为底物 ,获得了ee值为 82 %和收率为 98%的加成产物 .探讨了聚SalenD Ti(Ⅳ )上取代基对芳香醛硅腈化反应产物光学异构体选择性的影响 .在 2 0℃下 。As a versatile intermediate, chiral α-cyanohydrins can be synthesized by asymmetric trimethylsilylcyanation of aldehydes. Schiff base-Ti complexes have been proven to be excellent catalysts for this reaction. Polysalen-Ti (Ⅳ) complex was successfully used in asymmetric trimethylsilylcyanation of benzaldehyde and its substitutes. The adducts of trimethylsilylcyanation of 4-CH_3-C_6H_4CHO and 4-Cl-C_6H_4CHO were obtained with ee=82%, yield=93%, and ee=82%, yield=98%, respectively, at -40 ℃. The catalyst could be recycled for 5 times while maitaining its activity and enantioselectivity at 20 ℃.

关 键 词：芳香醛 不对称硅腈化 聚Salen 钛配合物 苯甲醛 光学异构体选择性 三甲基硅腈 催化剂 

分 类 号：O643.3[理学—物理化学]