Nitrile biotransformations for highly efficient and enantioselective syntheses of electrophilic oxiranecarboxamides.
Catalyzed by a nitrile hydratase/amidase-containing microbial Rhodococcus sp. AJ270 whole-cell catalyst, a number of racemic trans-2,3-epoxy-3-arylpropanenitriles 1 underwent rapid and efficient hydrolysis under very mild conditions to afford 2R,3S-2-arylglycidamides 2 in excellent yield with enantiomeric excess higher than 99.5%. The overall enantioselectivity of the biotransformations originated from the combined effects of a dominantly high 2S-enantioselective amidase and low 2S-enantioselective nitrile hydratase involved in the cell. The influence of the substrates on both reaction efficiency and enantioselectivity was also discussed in terms of steric and electronic effects.
Wang
Mei-Xiang
MX
Laboratory for Chemical Biology, Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China. mxwang@iccas.ac.cn
Lin
Shuang-Jun
SJ
Liu
Chu-Sheng
CS
Zheng
Qi-Yu
QY
Li
Ji-Sheng
JS
D000577:Amides / Q000032:analysis / Q000138:chemical synthesis*; D001711:Biotransformation; D002384:Catalysis; D005027:Ethylene Oxide / Q000031:analogs & derivatives* / Q000032:analysis / Q000138:chemical synthesis*; D006836:Hydro-Lyases / Q000378:metabolism*; D007700:Kinetics; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D012240:Rhodococcus / Q000201:enzymology*; D013237:Stereoisomerism
D000577:Amides; D009570:Nitriles; D006836:Hydro-Lyases; C048831:nitrile hydratase; D005027:Ethylene Oxide