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.

Studies on the Catalytic Promiscuity of Limonene Epoxide Hydrolases in the Non-hydrolytic Ring Opening of 1,2-Epoxides / I. Bassanini, E.E. Ferrandi, D. Monti, S. Riva. - In: CHEMBIOCHEM. - ISSN 1439-4227. - (2020). [Epub ahead of print]

Studies on the Catalytic Promiscuity of Limonene Epoxide Hydrolases in the Non-hydrolytic Ring Opening of 1,2-Epoxides

Bassanini I.;Riva S.
2020

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.
limonene epoxide hydrolases; enzyme promiscuity; epoxides; nucleophiles; organic solvents
Settore BIO/10 - Biochimica
16-mar-2020
CHEMBIOCHEM
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/739083
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