Facile synthesis of selenocarbamyl fluorides, selenoureas and their derivatives with [Me4N][SeCF3]

Abstract

Tetramethylammonium trifluoromethylselenate ([Me₄N][SeCF₃]) has been confirmed as an excellent precursor of selenofluorophosgene for amines in the preparation of selenocarbamoyl fluorides, selenoureas, and heterocycles under catalyst- and additive-free conditions. Reactions of [Me₄N][SeCF₃] with secondary amines at room temperature provided exclusively selenocarbamoyl fluorides in moderate to high yields, while the same reactions with primary amines afforded selenoureas in good yields. When [Me₄N][SeCF₃] was similarly mixed with amines containing adjacent amino, hydroxyl or thiol groups, five- and six-membered heterocycles were produced. The reaction featured simplicity, rapidness, high efficiency, a broad substrate scope, and good functional group tolerance, offering a convenient access to a variety of selenocarbonylated compounds, which were otherwise difficult to synthesize by other approaches.