The Single‐Component Flavin Reductase/Flavin‐Dependent Halogenase AetF is a Versatile Catalyst for Selective Bromination and Iodination of Arenes and Olefins**

Abstract Flavin‐dependent halogenases (FDHs) natively catalyze selective halogenation of electron rich aromatic and enolate groups. Nearly all FDHs reported to date require a separate flavin reductase supply them with FADH 2 , which complicates biocatalysis applications. In this study, we establish that the single component reductase/flavin dependent halogenase AetF catalyzes diverse set substrates using commercially available glucose dehydrogenase drive its activity. High site selectivity, activity on relatively unactivated substrates, high enantioselectivity for atroposelective bromination bromolactonization was demonstrated. Site‐selective iodination enantioselective cycloiodoetherification also possible AetF. The substrate reaction scope suggest it has potential greatly improve utility biocatalytic halogenation.