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有机化学
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有机化学 ›› 2010, Vol. 30 ›› Issue (11): 1695-1699. 上一篇    下一篇

研究论文

脂肪酶-酸性树脂耦合催化1-苯乙醇的动态动力学拆分

程咏梅，徐刚，吴坚平，杨立荣*   

  1. (浙江大学化学工程与生物工程系 杭州 310027)
  • 收稿日期:2010-03-13 修回日期:2010-05-11 发布日期:2010-06-17
  • 通讯作者: 程咏梅 E-mail:cymhope@zju.edu.cn
  • 基金资助:

    动态动力学拆分制备手性药物中间体的应用基础研究;高效脂肪酶调控机制及性能强化的基础研究;典型高效生物催化剂及其反应体系的开发;化学-酶法制备手性S-生物烯丙菊酯的关键技术研究

Dynamic Kinetic Resolution of 1-Phenylethanol Catalyzed by Lipase Coupled with Acid Resin

CHENG Yong-Mei, XU Gang, WU Jian-Ping, YANG Li-Rong   

  1. (Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027)
  • Received:2010-03-13 Revised:2010-05-11 Published:2010-06-17

PDF

1245

被引次数

5

发现了一种催化效率较高的消旋催化剂——CD550树脂, 其与脂肪酶耦合可成功催化1-苯乙醇的动态动力学拆分(DKR). 该树脂60 ℃下可将100 mmol/L (S)-1-苯乙醇于1.5 h内完全消旋. 当其应用于1-苯乙醇的DKR反应时, 通过采用结构较复杂的邻苯二酚二乙酸酯、间苯二酚二乙酸酯、3,5-二甲基苯酸乙酸酯作为酰基供体, 可有效抑制树脂催化的底物无选择性转酯化, 极大提高底物转化率和产物ee值. 以邻苯二酚二乙酸酯参与的DKR反应为例, 反应10 h, 转化率大于99%, eeP为90.5%.

关键词: 1-苯乙醇, 动态动力学拆分, 消旋, 酰基供体

A new and efficient dynamic kinetic resolution (DKR) process of 1-phenylethanol was developed with acid resin as racemization catalyst and lipase as resolution catalyst. Acid resin CD550 was shown to have excellent racemization activity and could racemize 100 mmol/L (S)-1-phenylethanol in 1.5 h at 60 ℃. When employing CD550 and complex acyl donors such as 1,2-diacetoxybenzene, 1,3-diacetoxybenzene and 3,5-dimethyl phenyl acetate instead of vinyl acetate as racemization catalyst and acyl donor respectively to the DKR of 1-phenylethanol, enantiomerically pure (R)-1-phenylethanol acetate could be obtained with excellent yield and ee values. During processing, the conversion and the selectivity of the DKR were successfully enhanced by using more complex acyl donors to inhibit the acid resin-catalyzed unslective transesterification. For instance, when 1,2-diacetoxybenzene as acyl donor, the conversion and the eep could reach above 99% and 90.5% after 10 h, respectively.

Key words: 1-phenylethanol, dynamic kinetic resolution, racemization, acyl donor