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Studies on the Catalytic Promiscuity of Limonene Epoxide Hydrolases in the Non‐hydrolytic Ring Opening of 1,2‐Epoxides
Author(s) -
Bassanini Ivan,
Ferrandi Erica Elisa,
Monti Daniela,
Riva Sergio
Publication year - 2020
Publication title -
chembiochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.05
H-Index - 126
eISSN - 1439-7633
pISSN - 1439-4227
DOI - 10.1002/cbic.201900694
Subject(s) - chemistry , nucleophile , epoxide , cyclohexene oxide , glycidol , hydrolysis , organic chemistry , catalysis , sodium azide , cyclohexene , substrate (aquarium) , medicinal chemistry , oceanography , geology
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.