Radical 1,3-Difunctionalization of β,γ-Unsaturated Ketones via Concomitant 1,2-Carbonyl Migration: An Entrance to β-SF

The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF5/β-CF3SF4 ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF5-containing compound 5 exhibits potential anticancer activity, underscoring the utility of this approach.