A Study of Stereoselective Hydrolysis of Symmetrical Diesters with Pig Liver Esterase

Abstract

Abstract Pig liver esterase‐(PLE) catalyzed hydrolysis of dimethyl esters of symmetrical dicarboxylic acids, including meso ‐diacids, cis ‐1,2‐cycloalkanedicarboxylic acids, and diacids with a prochiral center, was studied with 14 substrates. The products of these stereoselective hydrolyses are chiral monoesters of dicarboxylic acids, with an enantiomeric excess (e.e.) from 10% to 100%. Some of these optically active monoesters are valuable synthons in natural products synthesis. An additivity pattern of α‐ and β‐substituents with the glutaric esters on the stereoselectivity of enzymatic hydrolysis was observed. Analysis of the experimental results leads to a model of enzyme stereoselectivity of diester hydrolysis in which the substitution pattern at α‐ and β‐C‐atoms is found to determine the absolute configuration of the resulting monoester.