Superacid‐Catalyzed Trifluoromethylthiolation of Aromatic Amines

Upon activation under superacid conditions, functionalized tailor‐made N‐SCF₃ sulfenamides served as reagents for the trifluoromethylthiolation of aromatic amines. This method has a broad substrate scope and can be used for the late‐stage functionalization of complex molecules such as alkaloids or steroids. Mechanistic studies based on in situ low‐temperature NMR spectroscopy revealed the involvement of dicationic superelectrophilic intermediates.