催化学报 ›› 2011, Vol. 32 ›› Issue (7): 1275-1279.DOI: 10.3724/SP.J.1088.2011.10308

• 研究论文 • 上一篇    下一篇

L-脯氨酸修饰的 Ru-PPh3/γ-Al2O3 催化芳香酮不对称加氢反应

熊伟1,*, 刘德蓉1, 贾云1, 秦瑞香1, 邱会东1, 王金波1, 李贤均2   

  1. 1重庆科技学院化学化工学院, 重庆 401331; 2四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, 四川成都 610064
  • 收稿日期:2011-03-06 修回日期:2011-04-29 出版日期:2011-07-18 发布日期:2014-11-28

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by L-Proline-Modified Ru-PPh3/γ-Al2O3 Catalyst

XIONG Wei1,*, LIU Derong1, JIA Yun1, QIN Ruixiang1, QIU Huidong1, WANG Jinbo1, LI Xianjun2   

  1. 1College of Chemistry and Chemical Engineering, Chongqing University of Science and Technology, Chongqing 401331, China; 2Key Laboratory of Green Chemistry and Technology of Ministry of Education, Institute of Homogeneous Catalysis, College of Chemistry, Sichuan University, Chengdu 610064, Sichuan, China
  • Received:2011-03-06 Revised:2011-04-29 Online:2011-07-18 Published:2014-11-28

摘要: 以 L-脯氨酸为修饰剂, 研究了膦配体稳定的 Ru-PPh3/γ-Al2O3 催化剂催化芳香酮不对称加氢反应, 考察了不同稳定剂、L-脯氨酸浓度、KOH 浓度、反应温度和氢气压力等因素对加氢反应的影响. 结果表明, 天然手性化合物 L-脯氨酸对 Ru-PPh3/γ-Al2O3 催化剂具有较好的修饰作用, 在优化反应条件下, 苯乙酮加氢产物 (S)-α-苯乙醇对映选择性达 59.5%. L-脯氨酸不仅具有手性诱导作用, 而且与 KOH 之间存在协同作用. 催化剂循环使用 5 次, 产物对映选择性没有明显下降.

关键词: L-脯氨酸, 芳香酮, 不对称加氢, 钌, 负载型催化剂

Abstract: The asymmetric hydrogenation of aromatic ketones catalyzed by L-proline-modified Ru-PPh3/γ-Al2O3 was investigated. The effects of reaction conditions on the asymmetric hydrogenation of acetophenone were discussed in detail. The results indicated that natural chiral compound L-proline has a good modification effect on the Ru-PPh3/γ-Al2O3 catalyst. Under the optimum conditions, the conversion of acetophenone was up to 100%, and the enantioselectivity for the formation of (R)-phenyl ethanol was 59.5%. The synergistic effect between L-proline and KOH was observed. The chiral alcohol products could be easily separated by centrifugation. The catalyst was reused several times without remarkable change of enantioselectivity.

Key words: L-proline, aromatic ketone, asymmetric hydrogenation, ruthenium, supported catalyst