Combining Light Irradiation and Aldoxime Dehydratase for the Synthesis of Benzonitriles From Benzyl Alcohols Through Oxime Intermediates

Synthesis of oximes and nitriles from alcohols traditionally requires high temperatures, toxic reagents, and unfriendly solvents. Herein, the combination of photo‐ and biocatalytic processes is disclosed by first performing a photocatalytic oxidative oximation of benzyl alcohols to produce benzaldehyde oximes in the presence of hydroxylamine hydrochloride (75%–99% conversion after 4 h). Subsequently, enzymatic dehydration was carried out using the double mutant of the aldoxime dehydratase OxdF1 (L318F/F306Y) in a stepwise manner, which allowed obtaining benzonitriles (50%–73% isolated yield).