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

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (6): 1354.

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

李凯翔, 李晓红, 宋丽英, 吴鹏

华东师范大学化学系, 上海市绿色化学与化工过程绿色化重点实验室, 上海 200062

收稿日期:2010-11-04 修回日期:2011-03-28 出版日期:2011-06-10 发布日期:2011-05-10
通讯作者: 李晓红 E-mail:xhli@chem.ecnu.edu.cn
基金资助:
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.

Asymmetric Hydrogenation of α-Ketoesters on Chirally Modified Pt Catalysts Supported on MPC-61 Ordered Mesoporous Carbon

LI Kai-Xiang, LI Xiao-Hong*, SONG Li-Ying, WU Peng

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China

Received:2010-11-04 Revised:2011-03-28 Online:2011-06-10 Published:2011-05-10
Contact: LI Xiao-Hong E-mail:xhli@chem.ecnu.edu.cn
Supported by:
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.

摘要/Abstract

摘要： 采用氯铂酸乙醇溶液和水溶液为前体通过浸渍法分别制备了介孔碳材料MPC-61负载的质量分数为4%和10%的催化剂Pt/MPC-61，并利用XRD、TEM、N2气吸脱附和CO化学吸附等手段对催化剂进行了表征. 考察了经过手性分子辛可尼定修饰后的Pt/MPC-61催化剂在丙酮酸乙酯不对称氢化反应中的催化性能. 对于担载量4%的催化剂，以氯铂酸乙醇溶液为前体制备的催化剂因其具有较小的粒径和较高的分散度而表现出较高的活性，而以氯铂酸水溶液为前体制备的催化剂则具有较强的手性诱导能力. 前体经150 oC真空焙烧的催化剂上无论是转化率还是光学选择性均有所提高,水溶剂中的TOF值高达8820 h-1. 对于担载量10%的催化剂，在乙酸溶剂中对(R)-(+)-乳酸乙酯的光学选择性可以达到66% e.e..值得指出的是，担载量为4%的Pt/MPC-61催化剂表现出比商品化5 wt% Pt/C更高的催化活性. 还将担载量为4%的催化剂用于手性药物依那普利前体的不对称合成中，前体经150 oC真空焙烧的催化剂在乙酸溶剂中可以取得61% e.e.的光学选择性.

关键词: 介孔碳材料, 铂催化剂, 辛可尼定, a-酮酸酯, 不对称氢化

Abstract: 4% and 10% (mass fraction) Pt catalysts supported on MPC-61, a kind of ordered mesoporous carbon, were prepared 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-61catalysts proved to be efficient 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 better 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 H2PtCl6 showed higher chiral induction ability. The catalyst Cat-4Pt-W-150 that was calcined at 150 oC under vacuum gave higher conversion and higher enantioselectivity than Cat-4Pt-W did, the highest TOF reaching 8820 h-1 in water. A 66% ee 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 Pt/C catalyst, mainly due to the ordered mesoporous structure features of MPC-61 support. The 4% Pt catalysts supported on MPC-61 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% ee value of (R)-(+)-ethyl 2-hydroxyl-4-phenylbutyrate.

Key words: Ordered mesoporous carbon, Pt catalyst, Cinchonidine, a-Ketoesters, Asymmetric hydrogenation

TrendMD:

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. 高等学校化学学报, 2011, 32(6): 1354.

LI Kai-Xiang, LI Xiao-Hong*, SONG Li-Ying, WU Peng. Asymmetric Hydrogenation of α-Ketoesters on Chirally Modified Pt Catalysts Supported on MPC-61 Ordered Mesoporous Carbon. Chem. J. Chinese Universities, 2011, 32(6): 1354.

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