Unified Electrochemical eFluorination of Amines to Thiocarbamoyl Fluorides, N-trifluoromethyl Amines, and Carbamoyl Fluorides

A unified electrochemical eFluorination platform is reported for the divergent synthesis of three valuable fluorinated motifs directly from simple secondary amines: thiocarbamoyl fluorides (R₂NCSF), N -trifluoromethyl amines (R₂NCF₃), and carbamoyl fluorides (R₂NCOF). Using inexpensive and bench-stable reagents (Et₃N·3HF, CS₂, and KOH or DABCO), these transformations proceed in one pot under mild, open-air conditions, without solvent drying, degassing, or expensive reagents. The liquid, glass-compatible fluorine source Et₃N·3HF offers controlled reactivity and excellent safety, enabling a sustainable process with an eco-scale factor of ~ 70 that is readily scalable at low cost. The method exhibits broad substrate scope and functional-group tolerance, allowing late-stage fluorination of complex and bioactive molecules. Mechanistic investigations combining cyclic voltammetry, spectroscopy (¹⁹F NMR, UV–Vis), HRMS, XRD, SEM-EDX, and authentic intermediate analysis reveal a multistep pathway involving dithiocarbamate salt and thiuram intermediates as well as a bromide-mediated fluorination cascade leading to N -trifluoromethyl amines formation. This operationally simple, metal-free platform provides a safe, scalable, and versatile route to key fluorinated building blocks for drug discovery and materials chemistry.