Portal de Periódicos da CAPES

Nitrile Biotransformations for Highly Enantioselective Synthesis of Oxiranecarboxamides with Tertiary and Quaternary Stereocenters; Efficient Chemoenzymatic Approaches to Enantiopure α-Methylated Serine and Isoserine Derivatives

2005; American Chemical Society; Volume: 70; Issue: 7 Linguagem: Inglês

10.1021/jo0482615

1520-6904

Mei‐Xiang Wang, Gang Deng, De‐Xian Wang, Qi‐Yu Zheng,

Biochemical and Molecular Research

Biotransformations of a number of differently substituted and configured oxiranecarbonitriles using Rhodococcus sp. AJ270, a microbial whole-cell catalyst that contains nitrile hydratase/amidase, were studied. While almost all trans-configured 3-aryl-2-methyloxiranecarbonitriles and 2,3-dimethyl-3-phenyloxiranecarbonitrile were efficiently hydrated by the action of the less enantioselective nitrile hydratase, the amidase exhibited excellent 2S,3R-enantioselectivity against 2-methyl-3-(para-substituted-phenyl)oxiranecarboxamides. Under very mild conditions, biotransformations of nitriles provided an efficient and practical synthesis of 2R,3S-(−)-3-aryl-2-methyloxiranecarboxamides, electrophilic epoxides with tertiary and quaternary stereocenters, in excellent yield with enantiomeric excess greater than 99.5%. The synthetic applications of the resulting enantiomerically pure epoxides were demonstrated by convenient and straightforward syntheses of polyfunctionalized chiral molecules possessing a quaternary stereocenter such as R-(+)-2-hydroxy-2-methyl-3-phenylpropionic acid, 2R,3R-(−)-3-amino-2-hydroxy-2-methyl-3-phenylpropionic acid, and 2S,3S-(+)-2-amino-3-hydroxy-2-methyl-3-phenylpropionic acid, employing the regio- and stereospecific epoxide ring opening reactions of 2R,3S-(−)-2-methyl-3-phenyloxiranecarboxamide as the key steps.