Wistuba D, Schurig V
Institut für Organische Chemie der Universität, Tübingen, Germany.
Chirality. 1992;4(3):178-84. doi: 10.1002/chir.530040309.
The in vitro conversion of chiral aliphatic monoalkylsubstituted oxiranes into 1,2-diols catalyzed by epoxide hydrolase of rat liver microsomes occurs with substrate enantioselectivity and regioselectivity. Substrate enantioselectivity is generally low, and has the same sense, for methyloxirane, vinyloxirane, epichloro-, and epibromohydrin. In the hydrolysis of t-butyloxirane inhibitory effects are involved leading to a complex pattern of enantioselectivity. All investigated monosubstituted aliphatic oxiranes are hydrolyzed with high regioselectivity by nucleophilic attack of water at the unsubstituted ring carbon atom. The enantiomeric excess of the unreacted oxirane substrates and the diol metabolites formed were determined by complexation and inclusion gas chromatography.
大鼠肝微粒体环氧化物水解酶催化手性脂肪族单烷基取代环氧乙烷体外转化为1,2 -二醇的过程具有底物对映体选择性和区域选择性。底物对映体选择性通常较低，对于甲基环氧乙烷、乙烯基环氧乙烷、环氧氯丙烷和环氧溴丙烷具有相同的方向。在叔丁基环氧乙烷的水解中，存在抑制作用，导致对映体选择性的复杂模式。所有研究的单取代脂肪族环氧乙烷通过水在未取代环碳原子上的亲核进攻以高区域选择性进行水解。通过络合和包合气相色谱法测定未反应的环氧乙烷底物和形成的二醇代谢物的对映体过量。
