高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (9): 1758.

• 研究论文 • 上一篇    下一篇

奎宁修饰的纳米铑簇合物催化丙酮酸乙酯对映选择性加氢反应研究

熊伟1,2, 马红霞1, 陈华1, 黄艳轶1, 黄裕林1, 李贤均1, 黎星术3, 戚建英3, 陈新滋3   

  1. 1. 四川大学化学学院, 成都 610064;
    2. 西昌师范高等专科学校化学系, 西昌 615022;
    3. 香港理工大学应用生物及化学科技系, 香港九龙
  • 收稿日期:2001-08-03 出版日期:2002-09-24 发布日期:2002-09-24
  • 通讯作者: 李贤均(1938年出生),男,教授,博士生导师,从事有机金属络合催化研究.E-mail:scuulixj@mail.sc.cninfo.net E-mail:scuulixj@mail.sc.cninfo.net
  • 基金资助:

    香港理工大学ASD项目资助

Studies on the Enantioselective Hydrogenation of Ethyl Pyruvate Catalyzed by γ-Al2O3 Support Rhodium Nanocluster/Quinine

XIONG Wei1,2, MA Hong-Xia1, CHEN Hua1, HUANG Yan-Yi1, HUANG Yu-Lin1, LI Xian-Jun1, LI Xing-Shu3, QI Jian-Ying3, CHEN Xin-Zi3   

  1. 1. College of Chemistry, Sichuan University, Chengdu 610064, China;
    2. Department of Chemistry, Xichang Normal College, Xichang 615022, China;
    3. Department of Applied Biologyand Chemical Technology, Hong Kong Polytechnic University, Hong Kong, China
  • Received:2001-08-03 Online:2002-09-24 Published:2002-09-24

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被引次数

46

摘要： 研究了奎宁作手性修饰剂修饰的负载型纳米铑簇合物催化剂(Rh/PVP-γ-Al2O3)催化丙酮酸乙酯不对称氢化反应,在该反应中手性修饰剂奎宁不仅具有手性诱导作用,而且还有明显加速反应的作用;载体γ-Al2O3在促进提高催化剂活性和对映选择性方面也有很重要的影响.在优化的反应条件[20℃,7.0MPaH2,c(奎宁)=3.86×10-3mol/L,四氢呋喃作溶剂]下,丙酮酸乙酯不对称加氢的转化频率(TOF)为871h-1,对映选择性达到了54.7%;反应温度降低到3℃时,对映选择性达到59.2%.

关键词: 纳米铑簇合物, 丙酮酸乙酯, 奎宁, 对映选择性加氢

Abstract: In the asymmetric hydrogenation of ethyl pyruvate catalyzed by Rh/PVPand Rh/PVP-γ-Al2O3, quinine as a chiral modifier can not only induce the enantioselectivity but also greatly accelerate the reaction rate.When nanocluster of Rh/PVPis supported on γ-Al2O3, the catalytic activity and enantioselectivity increase obviously. Comparing the turnover frequency(TOF) and enantiomeric excess of R-(+)-ethyl lactate(e.e. value) of Rh/PVPwith Rh/PVP-γ-Al2O3, the TOF and e.e. value rise by a factor of 10.6 and 2.03, respectively. The results indicate that γ-Al2O3 plays a very important role in the asymmetric hydrogenation for the accelaration of the reaction and promoting the increase of enantioselectivity. It is possible that γ-Al2O3 is fovourable for the dispersion of Rh/PVPon the support surface and inhibits the aggregation of Rh/PVP. Under the optimum conditions of 20 ℃, 7.0 MPa H2 and 3.86×10-3 mol/L of quinine concentration in tetrahydrofuran, TOFand e.e. value using Rh/PVP-γ-Al2O3 as catalyst can reach 871h-1 and 54.7%, respectively. When reaction temperature decreases to 3 ℃, the e.e. value increases to 59.2%.

Key words: Rhodium nanocluster, Ethyl pyruvate, Quinine, Enantioselective hydrogenation

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