Organophotoredox Dioxygenation of Alkenes via ROH···F-Activated <i>N</i>-Alkoxyphthalimides

The generation and controlled reactivity of alkoxyl radicals remain challenging due to their high energy and tendency for β-scission or hydrogen atom transfer events. Herein, we report a photoredox-catalyzed dioxygenation of alkenes enabled by the activation of fluorinated <i>N</i>-alkoxyphthalimides through hydrogen-bonded aggregates with ROH···F. This transformation proceeds under mild, metal-free conditions using an organophotocatalyst and a simple alcohol, affording a diverse range of dialkoxylated products with high functional group tolerance and good scalability. Mechanistic studies─including UV-Vis spectroscopy, NMR, cyclic voltammetry, and Stern-Volmer quenching─reveal a radical/polar crossover pathway.