Wang Mei-Xiang, Lin Shuang-Jun
Center for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.
J Org Chem. 2002 Sep 6;67(18):6542-5. doi: 10.1021/jo0256282.
Catalyzed by the nitrile hydratase and the amidease in Rhodococcus sp. AJ270 cells under very mild conditions, a number of alpha-aryl- and alpha-alkyl-substituted DL-glycine nitriles 1 rapidly underwent a highly enantioselective hydrolysis to afford D-(-)-alpha-amino acid amides 2 and L-(+)-alpha-amino acids 3 in high yields with excellent enantiomeric excesses in most cases. The overall enantioselectivity of the biotransformations of nitriles originated from the combined effects of a high L-enantioselective amidase and a low enantioselective nitrile hydratase. The influence of the substrates on both reaction efficiency and enantioselectivity was also discussed in terms of steric and electronic effects. Coupled with chemical hydrolysis of D-(-)-alpha-phenylglycine amide, biotransformation of DL-phenylglycine nitrile was applied in practical scale to produce both D- and L-phenylglycines in high optical purity.
在非常温和的条件下，红球菌属AJ270细胞中的腈水合酶和酰胺酶催化多种α-芳基和α-烷基取代的DL-甘氨酸腈1迅速进行高度对映选择性水解，在大多数情况下以高收率和优异的对映体过量得到D-(-)-α-氨基酸酰胺2和L-(+)-α-氨基酸3。腈生物转化的整体对映选择性源自高L-对映选择性酰胺酶和低对映选择性腈水合酶的综合作用。还从空间和电子效应方面讨论了底物对反应效率和对映选择性的影响。结合D-(-)-α-苯基甘氨酸酰胺的化学水解，DL-苯基甘氨酸腈的生物转化被实际应用于以高光学纯度生产D-和L-苯基甘氨酸。
