Results
Title

Repurposing Iron‐ and 2‐Oxoglutarate‐Dependent Oxygenases to Catalyze Olefin Hydration.

Authors

Wang, Bingnan; Lu, Yong; Cha, Lide; Chen, Tzu‐Yu; Palacios, Philip M.; Li, Liping; Guo, Yisong; Chang, Wei‐chen; Chen, Chuo

Abstract

Mononuclear nonheme iron(II) and 2‐oxoglutarate (Fe/2OG)‐dependent oxygenases and halogenases are known to catalyze a diverse set of oxidative reactions, including hydroxylation, halogenation, epoxidation, and desaturation in primary metabolism and natural product maturation. However, their use in abiotic transformations has mainly been limited to C−H oxidation. Herein, we show that various enzymes of this family, when reconstituted with Fe(II) or Fe(III), can catalyze Mukaiyama hydration—a redox neutral transformation. Distinct from the native reactions of the Fe/2OG enzymes, wherein oxygen atom transfer (OAT) catalyzed by an iron‐oxo species is involved, this nonnative transformation proceeds through a hydrogen atom transfer (HAT) pathway in a 2OG‐independent manner. Additionally, in contrast to conventional inorganic catalysts, wherein a dinuclear iron species is responsible for HAT, the Fe/2OG enzymes exploit a mononuclear iron center to support this reaction. Collectively, our work demonstrates that Fe/2OG enzymes have utility in catalysis beyond the current scope of catalytic oxidation.

Subjects

OXYGENASES; ABSTRACTION reactions; HYDRATION; ALKENES; HALOGENASES; IRON

Publication

Angewandte Chemie, 2023, Vol 135, Issue 41, p1

ISSN

0044-8249

Publication type

Academic Journal

DOI

10.1002/ange.202311099