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有机化学
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有机化学 ›› 2004, Vol. 24 ›› Issue (8): 937-942. 上一篇    下一篇

研究论文

有机相中α-氰基-3-苯氧基苄醇乙酯的酶促不对称醇解反应

吴坚平a, 王龙根b, 杨立荣*,a   

  1. a浙江大学材料与化工学院生物工程研究所 杭州 310027
    b中化化工科学技术研究总院 北京 100011
  • 收稿日期:2004-01-03 修回日期:2004-03-11 接受日期:2004-04-13 发布日期:2022-09-20
  • 通讯作者: * E-mail: lryang@zju.edu.cn; Tel: +86-0571-87952363.
  • 基金资助:
    国家973计划(No. 2003CB716008)和国家自然科学基金重点(No. 20336010)资助项目.

Lipase-Catalyzed Asymmetric Alcoholysis of α-Cyano-3-phenoxybenzyl Acetate in Organic Media

WU Jian-Pinga, WANG Long-Genb, YANG Li-Rong*,a   

  1. aInstitute of Biochemical Engineering, College of Material Science andChemical Engineering, Zhejiang University, Hangzhou 310027
    bCentral Research Institute of China Chemical Science and Technology, Beijing 100011
  • Received:2004-01-03 Revised:2004-03-11 Accepted:2004-04-13 Published:2022-09-20

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研究了有机相中脂肪酶催化α-氰基-3-苯氧基苄醇乙酯(CPBAc)的不对称醇解反应,制备了S-α-氰基-3-苯氧基苄醇(S-CPBA).以脂肪酶Lipase AS为催化剂,四氢呋喃为反应介质,甲醇为酰基受体,对反应过程的各种影响因素进行了研究.得到该酶反应的较适反应条件为:温度为35～45 ℃,脱水溶剂加水量为0%～1%,摇床转速大于200 r/min,酯醇摩尔比大于1:0.5, CPBAc为337.08 mmol/L时需要10 mg/mL的酶量.然后对底物和产物抑制、产物稳定性以及酶的重复利用进行了研究.对酶催化反应过程的详细考察表明,在200 g/L的底物浓度下反应依然可以高效进行,反应约33 h, S-CPBA转化率可达49%左右,ee大于98%,剩余底物R-CPBAc的ee也大于95%.最后进行了反应放大实验,取得了较好的实验结果.

关键词: α-氰基-3-苯氧基苄醇乙酯, 有机相酶催化, 不对称醇解

The lipase-catalyzed asymmetric alcoholysis of α-cyano-3-phenoxybenzyl acetate (CPBAc) in organic solvents for the synthesis of S-α-cyano-3-phenoxybenzyl alcohol (S-CPBA) was studied. With lipaseAlcaligenes sp. as catalyst, Tetrahydrofuran as solvent and methanol as acylacceptor, the effects of temperature, water content, rotation speed, the molar ratioof ester to alcohol and the addition amount of lipase on the reaction were investigated. The optimal conditions were determined as 35～45 ℃, addition of 0%～1% water, rotation speed of 200 r/min,molar ratio of ester to alcohol at 1:0.5 and addition of 10 mg/mL lipase whenthe concentration of CPBAc was 337.08 mmol/L. Then the inhibition of substrateand product on the reaction, the stability of the product and the reuse of the lipase were also studied. The reaction processes under different substrate concentrations were examined carefully. The results showed that the reaction could becarried out effectively even at the high substrate concentration of 200 g/L under the optimal conditions. After reaction for 33 h, the conversion of S-CPBAreached about 49%, and the ee of S-CPBA and R-CPBAc exceeded 98%and 95%, respectively. The reaction was scaled up and good result was also achieved.

Key words: α-cyano-3-phenoxybenzyl acetate, enzyme catalysis in organic media, asymmetric alcoholysis