Biocatalytic desymmetrization of 3-substituted glutaronitriles by nitrilases. A convenient chemoenzymatic access to optically active (S)-Pregabalin and (R)-Baclofen

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• 作者：YiTao Duan (1)
  PeiYuan Yao (1)
  Jie Ren (1)
  Chao Han (1) (2)
  Qian Li (1)
  Jing Yuan (1)
  JinHui Feng (1)
  QiaQing Wu (1)
  DunMing Zhu (1)
  
• 关键词：enzymatic desymmetrization ; nitrilases ; (S) ; Pregabalin ; (R) ; Baclofen
• 刊名：SCIENCE CHINA Chemistry
• 出版年：2014
• 出版时间：August 2014
• 年：2014
• 卷：57
• 期：8
• 页码：1164-1171
• 全文大小：683 KB
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• 作者单位：YiTao Duan (1)
  PeiYuan Yao (1)
  Jie Ren (1)
  Chao Han (1) (2)
  Qian Li (1)
  Jing Yuan (1)
  JinHui Feng (1)
  QiaQing Wu (1)
  DunMing Zhu (1)
  
  1. National Engineering Laboratory for Industrial Enzymes and Tianjin Engineering Center for Biocatalytic Technology, Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, Tianjin, 300308, China
  2. College of Biotechnology, Tianjin University of Science and Technology, Tianjin, 300457, China
  
• ISSN：1869-1870

文摘

Desymmetrization of prochiral 3-substituted glutaronitriles offers a new approach to access (S)-Pregabalin and (R)-Baclofen. A number of nitrilases from diverse sources were screened with 3-isobutylglutaronitriles (1a) or 3-(4-chlorophenyl)glutaronitriles (1b) as the substrate. Some nitrilases were found to catalyze the desymmetric hydrolysis of 1a and 1b to form optically active 3-(cyanomethyl)-5-methylhexanoic acid (2a) and 3-(4-chlorophenyl)-4-cyanobutanoic acid (2b) with high enantiomeric excesse (ee), respectively. This cannot be achieved using traditional chemical hydrolysis. Among them, AtNIT3 generated (R)-2b, whereas BjNIT6402 and HsNIT produced the opposite (S)-enantiomer with high conversions and ee values. Not only the nitrilases showed different activities and stereoselectivities toward these 3-substituted glutaronitriles, the 3-substituent of the substrates also exerted great effect on the enzyme activity and stereoselectivity. (S)-2a and (S)-2b were prepared with high yields and ee values using BjNIT6402 and HsNIT as the biocatalysts, respectively. A straightforward Curtius rearrangement of (S)-2a and (S)-2b, followed by the acidic hydrolysis, afforded (S)-Pregabalin and (R)-Baclofen. This offers a new platform methodology for the synthesis of optically active β-substituted γ-amino acids of pharmaceutical importance.