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Freestanding Fe/α‐ketoglutarate‐dependent halogenases are oxidoreductases that catalyze the installation of halogen atoms into unactivated sp3‐hybridized carbon centers with high stereo‐ and regioselectivity. Since their discovery in 2014, a small number of indole alkaloid and amino acid halogenases have been identified and characterized. First enzyme engineering examples suggest that the accessible substrate range of these enzymes may be expanded through the use of rational enzyme design and directed evolution. Structural investigations of non‐heme iron halogenases acting on freestanding as well as tethered substrates are beginning to inform about the principles of the underlying halogenation mechanism. [ABSTRACT FROM AUTHOR]

Keywords: biocatalysis; C-H activation; enzyme engineering; Fe/alpha-KG-dependent halogenase; genome mining EN biocatalysis C-H activation enzyme engineering Fe/alpha-KG-dependent halogenase genome mining 1 1 1 06/12/20 20200610 NES 200610 B Freestanding Fe/ -ketoglutarate-dependent halogenases b are interesting development targets as they may serve as valuable tools for the synthesis of high-value compounds. Initial enzyme engineering examples indicate that the accessible substrate range of these enzymes may be expanded whereas their throughout biophysical characterization continues to inform about the principles governing the halogenation mechanism. Biocatalysis, C-H activation, enzyme engineering, Fe/alpha-KG-dependent halogenase, genome mining. [Extracted from the article]