An unusual beta-vinyl effect leading to high efficiency and enantioselectivity of the amidase, nitrile biotransformations for the preparation of enantiopure 3-arylpent-4-enoic acids and amides and their applications in synthesis.
Biotransformations of 3-arylpent-4-enenitriles catalyzed by Rhodococcus erythropolis AJ270, a nitrile hydratase/amidase-containing microbial whole-cell catalyst were studied, and an unusual beta-vinyl effect of the substrate on the biocatalytic efficiency and enantioselectivity of the amidase was observed. While 3-arylpent-4-enenitriles and 3-phenylpentanenitrile were efficiently hydrated by the action of the less R-enantioselective nitrile hydratase, the amidase showed greater activity and higher enantioselectivity against 3-arylpent-4-enoic acid amides than 3-arylpentanoic acid amides. Under very mild conditions, nitrile biotransformations provided an efficient synthesis of highly enantiopure (R)-3-arylpent-4-enoic acids and (S)-3-arylpent-4-enoic acid amides, and their applications were demonstrated by the synthesis of chiral gamma-amino acid, 2-pyrrolidinone, and 2-azepinone derivatives.
Gao
Ming
M
Beijing National Laboratory for Molecular Sciences, Laboratory of Chemical Biology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.
Wang
De-Xian
DX
Zheng
Qi-Yu
QY
Wang
Mei-Xiang
MX
D000577:Amides / Q000737:chemistry*; D000581:Amidohydrolases / Q000737:chemistry*; D001711:Biotransformation; D009570:Nitriles / Q000493:pharmacokinetics*; D013237:Stereoisomerism
D000577:Amides; D009570:Nitriles; D000581:Amidohydrolases; C019665:amidase