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Catalysts 2018, 8(8), 314; https://doi.org/10.3390/catal8080314

A Comparative Review on the Catalytic Mechanism of Nonheme Iron Hydroxylases and Halogenases

Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN, UK
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Received: 17 July 2018 / Revised: 25 July 2018 / Accepted: 30 July 2018 / Published: 31 July 2018
(This article belongs to the Special Issue Quantum Chemical Modelling of Enzymatic Reactions)
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Abstract

Enzymatic halogenation and haloperoxidation are unusual processes in biology; however, a range of halogenases and haloperoxidases exist that are able to transfer an aliphatic or aromatic C–H bond into C–Cl/C–Br. Haloperoxidases utilize hydrogen peroxide, and in a reaction with halides (Cl/Br), they react to form hypohalides (OCl/OBr) that subsequently react with substrate by halide transfer. There are three types of haloperoxidases, namely the iron-heme, nonheme vanadium, and flavin-dependent haloperoxidases that are reviewed here. In addition, there are the nonheme iron halogenases that show structural and functional similarity to the nonheme iron hydroxylases and form an iron(IV)-oxo active species from a reaction of molecular oxygen with α-ketoglutarate on an iron(II) center. They subsequently transfer a halide (Cl/Br) to an aliphatic C–H bond. We review the mechanism and function of nonheme iron halogenases and hydroxylases and show recent computational modelling studies of our group on the hectochlorin biosynthesis enzyme and prolyl-4-hydroxylase as examples of nonheme iron halogenases and hydroxylases. These studies have established the catalytic mechanism of these enzymes and show the importance of substrate and oxidant positioning on the stereo-, chemo- and regioselectivity of the reaction that takes place. View Full-Text
Keywords: inorganic reaction mechanisms; density functional theory; computational modelling; enzyme catalysis; quantum mechanics/molecular mechanics inorganic reaction mechanisms; density functional theory; computational modelling; enzyme catalysis; quantum mechanics/molecular mechanics
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Timmins, A.; de Visser, S.P. A Comparative Review on the Catalytic Mechanism of Nonheme Iron Hydroxylases and Halogenases. Catalysts 2018, 8, 314.

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