Transition-Metal-Free, Site-Selective C–F Arylation of Polyfluoroarenes via Electrophotocatalysis

Direct CAr–F arylation is effective and sustainable for synthesis of polyfluorobiaryls with different degrees of fluorination, which are important motifs in medical and material chemistry. However, with no aid of transition metals, the engagement of CAr–F bond activation has proved difficult. Herein, an unprecedented transition-metal-free strategy is reported for site-selective CAr–F arylation of polyfluoroarenes with simple (het)­arenes. By merging N,N-bis­(2,6-diisopropylphenyl)­perylene-3,4,9,10-bis­(dicarboximide)-catalyzed electrophotocatalytic reduction and anodic nitroxyl radical oxidation in an electrophotocatalytic cell, various polyfluoroaromatics (2F–6F and 8F), especially inactive partially fluorinated aromatics, undergo sacrificial-reagents-free C–F bond arylation with high regioselectivity, and the yields are comparable to those for reported transition-metal catalysis. This atom- and step-economic protocol features a paired electrocatalysis with organic mediators in both cathodic and anodic processes. The broad substrate scope and good functional-group compatibility highlight the merits of this operationally simple strategy. Moreover, the easy gram-scale synthesis and late-stage functionalization collectively advocate for the practical value, which would promote the vigorous development of fluorine chemistry.