N-Arylation of amides and anilines with aryl iodides was efficiently catalyzed by copper thiophenecarboxylate under ligandfree conditions with good to excellent yields. A variety of substituted aryl iodides, amides, anilines and 4-aminoantipyrine were found to be applicable to the simple catalytic system. Furthermore, some practical, unique secondary amides, such as N-arylacrylamides and 4-amido-N-phenylbenzamides, and 4-amino(N-phenyl)antipyrenes, which are difficult to obtain by the classical methods, were prepared. a Reaction conditions: iodobenzene (1a, 1.0 mmol), acrylamide (2a, 1.2 mmol), base (2.0 mmol), solvent (3.0 ml), under nitrogen. b Isolated yield. c H 2 O (1.0 mmol) was added to the reaction. Z.-J Quan et al. wileyonlinelibrary.com/journal/aoc Additional supporting information may be found in the online version of this article at the publisher' web-site. Scheme 1. A possible mechanism for the CuTC-catalyzed N-arylation.Ligand-free CuTC-catalyzed N-arylation Appl.