Transition‐Metal‐Free Synthesis of Highly Fluorinated Biphenyls by Nucleophilic Aromatic Substitution (S _N Ar) between Potassium Perfluorobenzoates and Polyfluoroarenes

Highly fluorinated biphenyls are valuable motifs in various applications. Traditional methods for their synthesis often require expensive catalysts, harsh conditions, and sensitive reagents. Herein, a practical, transition‐metal‐free strategy for the synthesis of highly fluorinated biphenyls is reported via nucleophilic aromatic substitution (S N Ar) between potassium perfluorobenzoates and polyfluoroarenes. This method through an operationally simple protocol, using bench‐stable nucleophiles, enabling efficient access to structurally diverse biphenyls. It offers broad substrate scope, good functional group tolerance, and operational simplicity, providing an alternative to existing methods.