Stereocontrolled Hydrolysis of the Linoleic Acid Monoepoxide Regioisomers Catalyzed by Soybean Epoxide Hydrolase

Soybean fatty acid epoxide hydrolase (EC 3.3.2.3) was found to possess remarkable and unique stereochemical features. After complete hydrolysis, this enzyme converts racemic or enantiomerically enriched cis-9,10-epoxy-12(Z)-octadecenoic and cis-12,13-epoxyocta-9(Z)-decenoic acids, i.e. the two regioisomers of linoleic acid monoepoxides, into their corresponding 9R, 10R- and 12R, 13R-dihydrodiols with a high enantiomeric excess (> 90%). A straightforward chiral-phase HPLC technique was developed that gives an easy access to the stereochemistry of these reaction products. These results are discussed in terms of a possible model for the substrate binding site of this enzyme.