Copper-catalyzed ortho-thiocyanation of aromatic amines

A copper-catalyzed direct ortho-Csp²–H thiocyanation of free anilines has been developed. This method employs stable and non-toxic ammonium thiocyanate as a thiocyanation source, and tert-butyl hydroperoxide as the oxidant, enabling the synthesis of ortho-thiocyanated anilines with good yields and broad substrate tolerance. Hitherto, no reports have been found in the literature for the ortho-thiocyanation of aromatic amines, making this reaction an important breakthrough in synthetic organic chemistry.