Halogenases: structures and functions

Recent trends in biocatalysis

“…Besides the vanadium-dependent haloperoxidases, other halogenating enzymes [324][325][326][327] could also provide plenty of opportunities in the enzymatic syntheses of terpenoids (and other natural products) as well as their derivatives.…”

Halogenases: a palette of emerging opportunities for synthetic biology–synthetic chemistry and C–H functionalisation

“…Greater structural understanding of these enzymes has enabled progress to be made in their rational redesign. 187,188 Such approaches combined with substrate walking methods 189 have enabled the utilisation of halogenases in the selective decoration of increasingly more complex substrates, as well as stabilising enzymes to operate at higher temperatures. 190 Engineering of the NHFeHals has also enabled their application to a broader series of substrates (see Section 2.2.4).…”

“…Greater structural understanding of these enzymes has enabled progress to be made in their rational redesign. 187,188 Such approaches combined Scheme 11 V-BrHPO catalysed terpene bromination and cyclisation event in snyderol biosynthesis. 184 Scheme 12 FDH AoiQ dichlorination and dimethylation of diaporthin 271.…”

A Promiscuous Halogenase for the Derivatization of Flavonoids

“…The generated hypohalous acid is then transferred from the FAD binding site to the substrate binding cavity through a 10 Å long channel [54]. In the substrate pocket, hypohalous acid is coordinated by the highly conserved active site lysine residue, which then performs halogenation according to electrophilic aromatic substitution mechanism [25]. The electron-rich aromatic ring of the substrate attacks the electrophilic chlorine species, leading to halogen attachment and disruption of the aromatic system.…”

“…Most of the halogenases involved in the biosynthesis of natural products belong to the family of flavin-dependent oxidoreductases [25]. These enzymes use salts present in aqueous solutions as halogen sources.…”