Discovery and Development of an Aerobic Radical Hydroxyarylation Reaction Using Aryl Halides, Olefins, and O₂

Herein, we report the development of a radical hydroxyarylation reaction through the coupling of an aryl radical, an olefin, and O₂. Photoredox activation of a silyl radical halogen atom abstractor enables mild aryl radical generation and reactivity in 5-<i>exo</i>, 6-<i>exo</i>, and dearomative cyclizations to synthesize a variety of hydroxylated semisaturated fused ring systems. Expansion of the substrate scope to include aryl bromide starting materials reveals the crucial role of iodide in the catalytic cycle.