Aerobic Baeyer‐Villiger Oxidation Catalyzed by Metal Corroles

Metal corrole catalyzed Baeyer‐Villiger oxidation reaction was successfully achieved for the first time. Among all tested Co, Mn, Fe and Cu complexes of 5, 10, 15‐Tris (pentafluorophenyl) corrole, Fe complex [Fe(tpfc)Cl] exhibited the best activity, and the highest yield was observed for six membered cyclic ketones. Preliminary results suggest that Fe(tpfc)Cl may act as an initiator for dehydrogenation of benzaldehyde to generate benzoyl radical, which will form peroxybenzoic acid under molecular oxygen atmosphere. The oxidation of Fe(tpfc)Cl catalyst by peroxybenzoic acid produces high‐valent iron‐oxo corrole intermediate. The iron‐oxo corrole is attacked by cyclohexanone to form a Criegee adduct, which will finally generate ϵ‐caprolactone product to finish the catalytic cycle. The 4 A‐MS additive may accelerate the production of perbenzoic acid and significantly improve the reaction yield. The conversion of cyclohexanone to ϵ‐caprolactone had been achieved by metal corrole catalyzed B−V oxidation reaction. It was found that iron corrole Fe(tpfc)Cl exhibited the best catalytic activity for B−V oxidation and the activity could be further enhanced by 4 A‐MS additive.