Deacylative Functionalization of Ketones via Radical-Triggered Alkyl–Acyl Bond Cleavage

Abstract Herein, we disclose a radical-triggered deacylative functionalization of ketones that proceeds efficiently under transition-metal-free and high-energy-light-free conditions. Readily accessible methyl ketones are harnessed to form pre-aromatic intermediates (PAIs), which undergo aromatization-promoted α-C–C bond scission to deliver versatile carbon-centered radicals. Leveraging this radical intermediate, a diverse range of deacylative reactions, including alkenylation, alkynylation, heteroarylation, and oxime etherification, were successfully achieved.