Synthesis of Trifluoromethylphosphines from Alkylphosphines

Despite their value as unique ligands, synthesizing trifluoromethylphosphines (TFMPhos) traditionally requires reactive precursors (bearing P–H, P–X, or P–Si bonds). Directly converting a P–C(sp3) into a P–CF3 bond remains a formidable challenge. Herein, we report a practical, transition-metal-free method for the direct conversion of alkylphosphines into TFMPhos using Togni’s reagent II and NaI. This operationally simple, mild protocol features broad functional group tolerance, providing versatile access to diverse TFMPhos derivatives.