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Abstract Cytochrome P450 OleT is a fatty acid decarboxylase that catalyzes the production of olefins with biofuel and synthetic applications. However, the relatively sluggish catalytic efficiency of the enzyme limits its applications. Here, we report the application of a novel class of benzene containing small molecules to improve the OleT activity. The UV‐Vis spectroscopy study and molecular docking results confirmed the high proximity of the small molecules to the heme group of OleT. Up to 6‐fold increase of product yield has been achieved in the small molecule‐modulated enzymatic reactions. Our work thus sheds the light to the application of small molecules to increase the OleT catalytic efficiency, which could be potentially used for future olefin productions.
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This content will become publicly available on April 16, 2026
Synergistic Photoenzymatic Anti-Markovnikov Hydroarylation of Olefins via Heteroaryl Radical Intermediates
Heteroaromatic alkylations are indispensable reactions for synthesizing biologically active molecules. The anti-Markovnikov hydroarylation of olefins using heteroaryl halides furnishes the product as a single regioisomer; however, catalytic variants are ineffective at controlling the stereochemical outcome of these reactions. Here, we report a synergistic photoenzymatic hydroarylation of olefins using flavin-dependent “ene”-reductases with ruthenium photoredox catalysts. Enzyme homologues were identified, which provide access to both product enantiomers in greater than 80% yield with up to 99:1 er. This method is effective for styrenyl- and unactivated alkenes, highlighting the generality of this approach. The highest yielding system involves a carboxylated photocatalyst with increased affinity for the enzyme. This work expands the types of radical intermediates that enzymes can use for stereoselective intermolecular coupling reactions.
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- Award ID(s):
- 2342328
- PAR ID:
- 10582923
- Publisher / Repository:
- Journal of the American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- ISSN:
- 0002-7863
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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