Studies on the Catalytic Promiscuity of Limonene Epoxide Hydrolases in the Non‐hydrolytic Ring Opening of 1, 2‐Epoxides. (30th March 2020)

• Record Type: Journal Article
• Authors: Bassanini, Ivan; Ferrandi, Erica Elisa; Monti, Daniela; Riva, Sergio
• Is Part Of: Chembiochem. Volume 21:Number 13(2020)
• Page Start: 1868
• Page End: 1874
• Publication Date: 2020-03-30
• Subjects: limonene epoxide hydrolases -- enzyme promiscuity -- epoxides -- nucleophiles -- organic solvents; Biochemistry -- Periodicals; Molecular biology -- Periodicals; Pharmaceutical chemistry -- Periodicals; 572
• DOI: 10.1002/cbic.201900694
• Languages: English
• ISSNs: 1439-4227

Abstract

Abstract: The non‐hydrolytic ring opening of 1, 2‐epoxides in the presence of limonene epoxide hydrolases (LEHs) and different nucleophiles has been investigated. Lyophilized, wild‐type LEHs were tested in selected water‐saturated organic solvents in the presence of cyclohexene oxide as substrate and different alcohols, thiols and primary amines as nucleophiles. Although the LEHs retained an appreciable catalytic activity under different reaction conditions, formation of the desired 1, 2‐substituted cyclohexanols was not observed. Alternatively, LEH variants incapable of performing the hydrolytic reaction were generated by site‐directed mutagenesis and tested in aqueous media in the presence of different water‐soluble nucleophiles and cyclohexene oxide. Under defined reaction conditions, an acceleration of up to about threefold of the spontaneous reaction rate was observed in the presence of sodium azide and potassium thiocyanate as nucleophiles. Abstract : Opening up : The possible promiscuous activity of limonene epoxide hydrolases in the non‐hydrolytic ring opening of 1, 2‐epoxides in the presence of different nucleophiles was investigated. The study was carried out by using either lyophilized, wild‐type biocatalysts in water‐saturated organic solvents or inactivated variants in aqueous media.