Highly Enantioselective Conversion of Racemic 1-Phenyl-1,2-ethanediol by Stereoinversion Involving a Novel Cofactor-Dependent Oxidoreduction System of Candida parapsilosis CCTCC M203011

Abstract

An economical and convenient biocatalytic process was developed for the preparation of (S)-1-phenyl-1,2-ethanediol (PED), which is a valuable chiral building block for pharmaceuticals and liquid crystals, by stereoselective microbial conversion from the corresponding racemate. As a result of screening bacteria, yeasts, and molds, the enantioselective conversion of racemic PED by Candida parapsilosis CCTCC M203011 was found to be the most efficient process to produce (S)-PED with high optical purity of 98% ee and yield of 92%. By detecting the intermediate produced in the reaction by GC−MS, it was suggested that (S)-enantiomer was produced from the intermediate identified as β-hydroxyacetophenone by asymmetric reduction after stereoselective oxidation of (R)-enantiomer to β-hydroxyacetophenone. After investigating the cofactor requirement and stereospecificity of the reaction catalyzed by the cell-free extract from C. parapsilosis CCTCC M203011, it was found that the stereoselective conversion involved the oxidation of (R)-PED to the intermediate with NADP+ as the cofactor and the reduction reaction that formed the product used NADH as the cofactor, which was catalyzed by a novel cofactor-dependent oxidoreduction system. The NADP+-dependent (R)-specific alcohol dehydrogenase involved in stereoinversion was purified from C. parapsilosis CCTCC M203011, which has a relative molecular mass of 45kD.

The effect of deep eutectic solvents on the asymmetric hydrolysis of styrene oxide by mung bean epoxide hydrolases

“…Chiral styrene glycol, namely (S) or (R)-1-phenyl-1,2-ethanediol (PED), is used as a crucial and multipurpose chiral building block for synthesis of pharmaceuticals, pesticides and liquid crystal materials (Chen et al 2012a). (R)-PED is a vital synthon for the synthesis of chiral β-adrenergic receptor blockers, antiarrhythmic drugs, and (S)-PED can be employed for the synthesis of production of chiral bisphosphines and the chiral initiator of selective polymerization (Nie et al 2004). In many methods for the synthesis of vicinal diols, epoxide hydrolases are often applied to catalyze the asymmetric hydrolysis of epoxides because of economy and convenience (Yu et al 2013).…”

Purification, Characterization, Gene Cloning, and Expression of a Novel Alcohol Dehydrogenase with Anti-Prelog Stereospecificity from Candida parapsilosis

“…In a previous study, we found that Candida parapsilosis CCTCC M203011 efficiently catalyzed the deracemization of racemic 1-phenyl-1,2-ethanediol (PED) to an S-enantiomer (24), which is a versatile chiral building block in organic synthesis (11,21). This reaction process of stereoinversion involves two steps, the oxidation step of (R)-PED to the intermediate (2-hydroxyacetophenone) by an R-specific alcohol dehydrogenase and the reduction step of the intermediate to (S)-PED (24).…”

“…This reaction process of stereoinversion involves two steps, the oxidation step of (R)-PED to the intermediate (2-hydroxyacetophenone) by an R-specific alcohol dehydrogenase and the reduction step of the intermediate to (S)-PED (24). The second step of asymmetric reduction is an anti-Prelog-type reaction involving an alcohol dehydrogenase with unusual stereospecificity (CPADH) (2, 22) (see Fig.…”

“…The microorganism C. parapsilosis CCTCC M203011 from the China Center for Type Culture Collection (CCTCC, Wuhan, China) was incubated as described previously (24). Then, the culture (100 ml), grown for 24 hours, was used as an inoculum in a 5-liter fermentor containing 3 liters of medium.…”

Biocatalytic oxidative kinetic resolution of (±)-4-(chlorophenyl)phenylmethanol by Nocardia corallina B-276

“…Deracemization of secondary alcohols through the stereoinversion of one alcohol enantiomer, has been observed in the presence of growing or resting cells, using *Corresponding author one (Comasseto et al 2004;Nie et al 2004;Padhi et al 2006;Vaijayanthi et al 2007;Yamada-Onodera et al 2007) or two different microorganisms (one for oxidation and the other for reduction) (Fantin et al 1995). Then, Sterigmatomyces elviae DSM 70852; Candida parapsilosis CCTCC M203011; C. parapsilosis ATCC 7330; Aspergillus terreus CCT 4083; A. terreus CCT 3320 were usedrespectively.…”