Organophosphorus fluorides are valuable motifs in chemical biology, medicinal chemistry, and synthesis, yet their preparation commonly relies on costly or operationally demanding fluorinating reagents. Herein, we describe a constant-current electrochemical oxidative fluorination of phosphine oxides using sulfur hexafluoride (SF₆) as the fluorine source. A range of diaryl and alkyl-substituted phosphine oxides is converted to the corresponding P(O)-F products in moderate to good isolated yields, reaching up to 72%. The transformation is proposed to combine cathodic single-electron reduction of SF₆, which furnishes fluoride-containing reduced fragments, with anodic oxidation of the phosphine oxide. Fluoride capture of the resulting phosphinoyl radical cation, followed by proton-coupled electron transfer, furnishes the P(O)-F bond. This study provides an electrode-driven route to use a persistent fluorinated greenhouse gas as a fluorine feedstock for organophosphorus synthesis.

Key words: sulfur hexafluoride, electrochemistry, oxidative fluorination, phosphine oxides, phosphorus-fluorine bond