9KUH

Co-crystal structure of wild-type OYE2 with 2-(prop-1-en-2-yl)pyridine

This is a non-PDB format compatible entry.

Summary for 9KUH

• Entry DOI: 10.2210/pdb9kuh/pdb
• Descriptor: NADPH dehydrogenase 2, FLAVIN MONONUCLEOTIDE, 2-prop-1-en-2-ylpyridine (3 entities in total)
• Functional Keywords: old yellow enzyme 2, 2-isopropenylpyridine, oxidoreductase
• Biological source: Saccharomyces cerevisiae S288C (Baker's yeast)
• Total number of polymer chains: 4
• Total formula weight: 182210.62

Authors

Wu, D.S.,Yang, J. (deposition date: 2024-12-03, release date: 2025-09-03)

Primary citation

Wu, D.,Sun, Z.,Wang, S.,Yang, J.,He, J.,Lei, X.
Enantioselective Radical Hydrocyanoalkylation of Alkenes via Photoenzymatic Catalysis.
Jacs Au, 5:3625-3631, 2025

PubMed Abstract: Organic nitriles are significant in pharmaceuticals, agrochemicals, cosmetics, and materials. Although numerous cyanidation methods have been developed, more eco-friendly and green protocols for manufacturing alkyl nitriles are in high demand. Here, we report a photoenzymatic enantioselective intermolecular hydrocyanoalkylation of alkenes catalyzed by flavin-dependent "ene"-reductases. The discovery of stereocomplementary enzymes that provide access to both enantiomers of the high-value nitriles further showcases the synthetic applications of this method. Radical trapping, isotopic labeling, and spectroscopic experiments have elucidated the formation of a charge transfer complex at the protein active site. The single-electron reduction of the cyanoalkyl radical precursor by flavin hydroquinone yields a cyanoalkyl radical, which then undergoes intermolecular radical addition. This active site can stereoselectively control the radical-terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic nitriles. This work further expands the reactivity repertoire of biocatalytic transformations via non-natural radical mechanisms.

PubMed: 40747066
DOI: 10.1021/jacsau.5c00633

Experimental method

X-RAY DIFFRACTION (3.43 Å)