Practical and divergent electrochemical access to thiocarbamoyl fluorides and N-trifluoromethyl amines from secondary amines.

We report a practical and divergent electrochemical method for converting simple secondary amines into thiocarbamoyl fluorides and N-trifluoromethyl amines. Using inexpensive, bench-stable reagents, including Et₃N·3HF and CS₂, these one-pot transformations proceed under mild, open-air conditions without solvent drying, degassing, inert atmosphere, or stoichiometric silver reagents. By tuning the reaction conditions, the same general strategy provides either product class in moderate to excellent yields across a broad substrate scope, with high functional-group tolerance and applicability to late-stage modification of complex bioactive molecules. The method is readily scalable and offers a practical alternative to existing fluorination approaches that rely on hazardous or costly reagents. Mechanistic studies combining cyclic voltammetry, ¹⁹F NMR spectroscopy, UV-Vis spectroscopy, HRMS, XRD, SEM-EDX, authentic intermediate analysis, and DFT calculations support a multistep pathway involving dithiocarbamate salts and thiuram intermediates, followed by bromide-assisted fluorination. This operationally simple, metal-free platform provides practical access to valuable fluorinated nitrogen-containing building blocks for synthesis, medicinal chemistry, and materials science.