Under indium Lewis acid catalysis, electron-rich five-membered heteroaryl electrophiles fused with/without a benzene ring were found to couple with amines to produce heteroarylamines with broad structural diversity. The heteroarylamine formation proceeds through the cleavage of a heteroarylÀOMe bond by the nucleophilic attack of the amine based on the nucleophilic aromatic substitution (S N Ar) reaction. In contrast to the corresponding traditional S N Ar amination, the present S N Ar-based heteroaryl amination can be performed without relying on both heteroaryl electrophiles with electron-withdrawing groups and nucleophilicity-enhanced metal amides. High compatibility towards the functional groups such as NO 2 , Br, I, CF 3 , CN, CO 2 Et, pyridyl, thiazolyl, C=C, and OH groups was observed, thus showing the practicality and reliability of this method. Mechanistic studies indicated that a carbonÀindium bond is likely to be formed on the heteroaryl ring during the process. Scheme 3. Indium-catalyzed S N Ar amination of 3,4-dimethoxythiophene with aniline.Scheme 4. Indium-catalyzed S N Ar amination of 3-bromo-4methoxythiophene with aniline.Scheme 5. Indium-catalyzed tandem S N Ar reaction of 2methoxythiophene with N-methyl-p-toluidine.

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