Photocatalytic Decyanative Borylation of Dicyanoarenes Enabled by Radical-Radical Coupling.

Cyanoarenes are important scaffolds in pharmaceutical and materials science and serve as versatile building blocks in synthetic chemistry. Herein, we report an orthogonal strategy for the decyanative borylation of dicyanoarenes via radical-radical coupling between amine-ligated boryl radicals and dicyanoarene-derived radical anions, enabled by an oxidative quenching photoredox cycle. Importantly, the resulting amine-borane adducts readily engage in Suzuki-Miyaura cross-couplings with aryl halides, including late-stage functionalization of bioactive compounds.