Copper-catalyzed N–H bond chalcogenation of anilines†

The chalcogen–nitrogen bond (X–N, where X = S, Se) is a key chemical motif in many structures, including inorganic and organic materials, catalysts, protein mimics, and pharmaceuticals. Consequently, developing mild and general methods for constructing N–S and N–Se bonds is important in organic synthesis. Herein, we have developed a novel copper-catalyzed approach to form N–S/N–Se bonds by coupling amines with 1,2-diphenyl disulfide or diphenyl diselenide. The disclosed platforms demonstrate excellent substrate scope, delivering the desired products in good to excellent yields, and are readily amenable for scale-up. The configuration of the product was confirmed through single-crystal X-ray diffraction analysis. Hitherto, no prior reports have been found in the literature for forming N–Se bonds making this reaction an important breakthrough in synthetic organic chemistry.