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TiO2负载的纳米铑簇合物催化丙酮酸乙酯不对称氢化反应的研究

Studies on the Asymmetric Hydrogenation of Ethyl Pyruvate Catalyzed by TiO2 Supported Rhodium Nanocluster

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【作者】 熊伟黄裕林马红霞陈华黎耀忠李蕾蕾程溥明李贤均

【Author】 XIONG, Wei a,b HUANG, Yu Lin a MA, Hong Xia a CHEN, Hua a LI, Yao Zhong a LI, Lei Lei a CHENG, Pu Ming a LI, Xian Jun , a ( a Department of Chemistry, Sichuan University, Chengdu 610064) ( b Department of Chemistry, Xichang Normal College, Xichang 615022)

【机构】 四川大学化学学院四川大学化学学院 成都610064西昌师范高等专科学校化学系西昌615022成都610064成都610064

【摘要】 研究了辛可尼定作手性修饰剂修饰的负载型纳米铑簇合物催化剂 (0 5 %Rh/PVP TiO2 )催化丙酮酸乙酯不对称氢化反应 ,在该反应中手性修饰剂辛可尼定不仅具有对产物生成的手性诱导作用 ,而且对反应具有明显加速作用 ;在优化反应条件后 ,反应的TOF和对映选择性分别可以达到 5 8 0min-1和 61 9%e e ..

【Abstract】 In the asymmetric hydrogenation of ethyl pyruvate catalyzed by 0 5% Rh/PVP TiO 2, the chiral modifier cinchonidine not only induces the enantioselectivity, but also accelerates the reaction rate greatly. A promotion effect of TiO 2 for the asymmetric hydrogenation is observed, when the modified rhodium nanoclusters are supported on TiO 2. The results show that TOF increase from 15 7 to 58 6 min -1 and e e . values of R (+) ethyl lactate increase from 42 2% to 60 0% in the hydrogenation of ethyl pyruvate. This suggests that TiO 2 is favourable for the dispersion of Rh/PVP and its stabilization on the support surface. Under the optimum conditions: 298 K, p H 2 =6 0 MPa, 4 3×10 -3 mol/L cinchonidine in THF, ethyl pyruvate/rhodium=942 (molar ratio), TOF and e e . value are 58 6 min -1 and 61 9%, respectively.

  • 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,2003年06期
  • 【分类号】O643.3
  • 【被引频次】22
  • 【下载频次】237
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