Visible-Light-Induced Radical Substitution of Unactivated Alkenes with β,β-Difluoroenol Sulfonates for the Synthesis of α,α-Difluoroketones

Herein, we disclose a visible-light-induced radical substitution between alkylzirconium intermediates and β,β-difluoroenol sulfonates. In this protocol, alkylzirconium species are generated <i>in situ</i> from unactivated alkenes and undergo photolytic homolysis to furnish alkyl radicals, which subsequently add to β,β-difluoroenol sulfonates to deliver α,α-difluoroketones. This photocatalyst-free method proceeds under mild conditions, exhibits broad substrate scope, and is readily to scale up. Given these features, the strategy offers a practical platform for the synthesis and late-stage diversification of pharmaceutically relevant difluorinated motifs.