The Single‐Component Flavin Reductase/Flavin‐Dependent Halogenase AetF is a Versatile Catalyst for Selective Bromination and Iodination of Arenes and Olefins. Issue 51 (22nd November 2022)

• Record Type: Journal Article
• Authors: Jiang, Yuhua; Snodgrass, Harrison M.; Zubi, Yasmine S.; Roof, Caitlin V.; Guan, Yanfei; Mondal, Dibyendu; Honeycutt, Nicholas H.; Lee, Johnny W.; Lewis, Russell D.; Martinez, Carlos A.; Lewis, Jared C.
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 51(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-11-22
• Subjects: Atroposelectivity -- C−H Functionalization -- Flavin Dependent Halogenase -- Halocyclization -- Iodinase; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202214610
• Languages: English
• ISSNs: 1433-7851

Abstract

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 to supply them with FADH2, which complicates biocatalysis applications. In this study, we establish that the single component flavin reductase/flavin dependent halogenase AetF catalyzes halogenation of a diverse set of substrates using a commercially available glucose dehydrogenase to drive its halogenase activity. High site selectivity, activity on relatively unactivated substrates, and high enantioselectivity for atroposelective bromination and bromolactonization was demonstrated. Site‐selective iodination and enantioselective cycloiodoetherification was also possible using AetF. The substrate and reaction scope of AetF suggest that it has the potential to greatly improve the utility of biocatalytic halogenation. Abstract : The single component flavin reductase/flavin dependent halogenase AetF catalyzes halogenation of a diverse set of substrates. High site selectivity, activity on relatively unactivated substrates, and high enantioselectivity for atroposelective bromination and bromolactonization was demonstrated. Site‐selective iodination and enantioselective cycloiodoetherification was also possible using AetF.