Radical 1,3-Difunctionalization of β,γ-Unsaturated Ketones via Synergistic LMCT and RLT Photocatalysis.

We report herein a simple and general photoinduced iron-catalyzed method that combines 1,2-functional group migration (1,2-FGM) with ligand-to-metal charge transfer (LMCT) and radical ligand transfer (RLT) to broaden the reaction profiles of alkene 1,3-difunctionalization. Based on this synergistic concept, the first 1,3-diazidation and 1,3-dichlorination of β,γ-unsaturated ketones via 1,2-carbonyl migration have been developed, providing a versatile means to access various 1,3-diazides and 1,3-dichlorides. These reactions feature a broad substrate scope, high regioselectivity, and good functional group tolerance. The late-stage derivatization of complex molecules, large-scale synthesis, and facile postmodification of products demonstrate their significant application potential.