物理化学学报 >> 2007, Vol. 23 >> Issue (04): 479-483.doi: 10.1016/S1872-1508(07)60031-X

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(1S, 2S)-DPEN修饰的负载型钌-铑双金属催化剂催化苯乙酮及其衍生物的不对称加氢

刘德蓉; 熊伟; 杨朝芬; 王金波; 陈华; 李瑞祥; 李贤均   

  1. 四川大学化学学院有机金属络合催化研究所, 绿色化学及技术教育部重点实验室, 成都 610064; 重庆科技学院化学与生物工程学院, 重庆 400050
  • 收稿日期:2006-09-05 修回日期:2006-11-11 发布日期:2007-04-05
  • 通讯作者: 李瑞祥 E-mail:sculiruixiang@163.com

Asymmetric Hydrogenations of Acetophenone and Its Derivatives over RuRh/γ-Al2O3 Modified by (1S, 2S)-DPEN and PPh3

LIU De-Rong; XIONG Wei; YANG Chao-Fen; WANG Jin-Bo; CHEN Hua; LI RUI-Xiang; LI Xian-Jun   

  1. Key Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, P. R. China; College of Chemical and Biological Engineering, Chongqing College of Science and Technology, Chongqing 400050, P. R. China
  • Received:2006-09-05 Revised:2006-11-11 Published:2007-04-05
  • Contact: LI RUI-Xiang E-mail:sculiruixiang@163.com

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摘要： 制备了以三苯基膦(PPh3)作为助剂的Ru-Rh/γ-Al2O3 催化剂, 在氢氧化钾的异丙醇溶液中, 用(1S, 2S)-DPEN [(1S, 2S)-1,2-diphenylethane-1,2-diamine]作手性修饰剂对苯乙酮及其衍生物进行不对称催化加氢, 此催化剂表现出较高的催化活性和良好的对映选择性. 优化反应条件, 苯乙酮、乙基苯基酮和异丙基苯基酮的转化率分别达到92.5%, 95.9%, 100%, 生成(R)-构型产物的ee值分别达到79.6%、81.2%和81.4%.

关键词: 钌, 铑, 双金属催化剂, 苯乙酮, 不对称加氢

Abstract: The asymmetric hydrogenations of acetophenone and its derivatives over the bimetallic catalyst RuRh/γ-Al2O3 modified by PPh3 and(1S, 2S)-DPEN [(1S, 2S)-1,2-diphenylethane-1,2-diamine]were studied. The effects of the concentration of KOH, temperature, ratio of ruthenium to rhodium, and the concentration of diamine on the asymmetric hydrogenation of acetophenone were investigated in detail. The results showed that this catalyst system had high activity and moderate enantioselectivity for the asymmetric hydrogenation of acetophenone and its derivatives. Under the optimum conditions, the conversions of acetophenone, ethylphenylketone, and isopropylphenylketone were up to 92.5%, 95.9%, and 100%, and the enantioselectivities for the formation of (R)-aromatic alcohols were 79.6%, 81.2%, and 81.4%, respectively.

Key words: Ruthenium, Rhodium, Bimetallic catalyst, Acetophenone, Asymmetric hydrogenation