Divergent Transformation of Diarylethanones via Anodic Oxidation and Electrochemical Baeyer–Villiger Oxidation for Scalable Synthesis of α-Acyloxyketones

A divergent electrochemical transformation of diarylethanones using molecular oxygen and electricity as green oxidants provides a sustainable and scalable strategy for synthesizing α-acyloxyketone compounds. Mechanistic studies reveal bromide-mediated generation of a benzyl radical cation intermediate, which undergoes divergent reaction pathways: (i) anodic oxidation to a benzyl cation or (ii) reaction with cathodically generated O₂^•- followed by Baeyer-Villiger oxidation to a carboxylate anion.