Phosphinylation of Non‐activated Aryl Fluorides through Nucleophilic Aromatic Substitution at the Boundary of Concerted and Stepwise Mechanisms

Abstract Non‐activated aryl fluorides reacted with potassium diorganophosphinites through a nucleophilic aromatic substitution (S N Ar) reaction. Remarkably, both electron‐neutral and electron‐rich aryl fluorides participated in the reaction with substantially stabilized anionic P nucleophiles to form the corresponding tertiary phosphine oxides. Quantum chemical calculations suggested a nucleophile‐dependent mechanism that involves both concerted and stepwise S N Ar reaction pathways.