高等学校化学学报2011，Vol.32Issue(6)：1354-1359,6.
手性修饰的介孔碳材料MPC-61负载铂催化剂上α-酮酸酯的不对称氢化反应
Asymmetric Hydrogenation of α-Ketoesters on Chirally Modified Pt Catalysts Supported on MPC-61 Ordered Mesoporous Carbon
摘要
Abstract
The Pt catalysts with mass fractions of 4％ and 10％ were supported on MPC-61, a kind of ordered mesoporous carbon, by an impregnation method using two different Pt precursors, ethanolic solution and aqueous solution of H2PtCl6. These Pt/MPC-61 catalysts were characterized by XRD, N2-sorption, TEM and CO chemisorption. The Pt/MPC-61 catalysts were applied in the asymmetric hydrogenation of ethyl pyruvate after chirally modified with cinchonidine. The Cat-4Pt-E catalyst derived from the ethanolic solution of H2PtCl6 afforded higher conversions of ethyl pyruvate due to smaller Pt particle size with higher Pt dispersion. While the Cat-4Pt-W catalysts derived from the aqueous solution of H2 PtCl6 showed higher chiral induction ability.The catalyst Cat-4Pt-W-150, which was calcined at 150 ℃ under vacuum, gave higher conversion and enantioselectivity than Cat-4Pt-W did, the highest TOF reaching 8820 h - 1 in water. A 66％ e. e. value was furnished by Cat-10Pt-E catalyst in acetic acid. In particular, the Cat-4Pt-W catalyst showed superior catalytic activity to the commercial 5％ (mass fraction) Pt/C catalyst, mainly due to the ordered mesoporous structure feature of MPC-61 support. Cat-4Pt-W can also be reused for more than 10 times without distinct loss of activity or enantioselectivity. The 4％ Pt/MPC-61 catalysts can also be effectively applied in the asymmetric hydrogenation of ethyl 2-oxo-4-phenylbutyrate, of which the hydrogenation product can be used to produce A. C. E inhibitors.Under the optimal conditions, the catalyst Cat-4Pt-W-150 gave a 61％ e. e. value of (R)-( + )-ethyl 2-hy-droxyl-4-phenylbutyrate in acetic acid.关键词
介孔碳材料/铂催化剂/辛可尼定/α-酮酸酯/不对称氢化Key words
Ordered mesoporous carbon/ Pt catalyst/ Cinchonidine/ α-Ketoesters/ Asymmetric hydrogenation分类
化学化工引用本文复制引用
李凯翔,李晓红,宋丽英,吴鹏..手性修饰的介孔碳材料MPC-61负载铂催化剂上α-酮酸酯的不对称氢化反应[J].高等学校化学学报,2011,32(6):1354-1359,6.基金项目
国家自然科学基金(批准号:20703018)、国家"九七三"计划项目(批准号:2006CB202508)和上海市科委科技启明星人才计划项目(批准号:08QA1402700)资助. （批准号:20703018）
