Control of Selectivity in FeCl3‐Catalyzed Aerobic Oxidation of Cycloketones

Abstract The FeCl 3 ‐catalyzed aerobic oxidation of ketones always gives rise to the α‐C−C cleavage product, having challenges to afford hydroxyl keto compounds. Here we report an effective control of the main product from keto acid to α‐hydroxyl ketone, by reducing the concentration of FeCl 3 catalyst, together with the use of DMSO as the solvent. In addition, mechanistic investigations suggested the same FeCl 3 ‐coordinated peroxide intermediate for both hydroxylation and C−C cleavage routes, and emphasize the role of DMSO as both ligand and reductant. This work provides a new approach for selective aerobic oxidation under Lewis acid catalysis.