A Heteroarylamine Library: Indium‐Catalyzed Nucleophilic Aromatic Substitution of Alkoxyheteroarenes with Amines

Abstract

Abstract 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 heteroaryl−OMe 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 carbon−indium bond is likely to be formed on the heteroaryl ring during the process. magnified image