2-Arylsulfanyl anilines are sub-units in a considerable number of the functional materials, the biologically important natural products and pharmaceuticals. Traditional methods required of such conditions as long steps or high temperature (≥150 ℃) and strong base, which lowered the yield of the products and limited the scope of the starting materials. In this paper, a highly general, experimentally simple, and inexpensive catalyst system was developed for the synthesis of 2-arylsulfanyl anilines by using 10 mol% CuI as catalyst, 20 mol% L-proline as ligand, and K₂CO₃ as base. And the existence of an ortho substitution effect caused by the NHCOCF₃ group promoted the reaction to carry out at the temperature as low as 60 ℃ in good to excellent yields.

Key words: copper reagent, 2-arylsulfanyl aniline, coupling, catalyst, ortho substitution effect