Nickel-Catalyzed C–H (Poly)addition of Alkenes and Alkynes with Polyfluoroarenes Enabled by an Unsymmetric N-Heterocyclic Carbene

Fluorinated small molecules and polymers are widely used in pharmaceuticals, agrochemicals, and materials science. Yet, their unified, highly efficient preparation from abundant feedstocks with excellent atom-, step-, and redox-economy remains elusive. Herein, we report a highly regioselective hydroarylation of diverse alkenes with polyfluoroarenes. This transformation is mediated by a rationally designed unsymmetric N-heterocyclic carbene (NHC) ligand, whose distinct steric profile accelerates both C–H activation and reductive elimination, affording superior reactivity and selectivity. Furthermore, this catalytic paradigm is extended to the direct C–H polyaddition of dienes and diynes, yielding copolymers with exceptional thermal stability and tunable fluorescence properties. Notably, this protocol aligns with the principles of sustainable chemistry, characterized by 100% atom economy, high step economy, and the absence of pre-functionalized reagents. This study establishes a versatile platform for the C–H functionalization and polymerization of polyfluoroarenes, paving the way for advancing polymer synthesis via C–H polyaddition strategies.