Copper-containing MOFs are found to be active, stable and reusable solid catalysts for three-component couplings of amines, aldehydes and alkynes to form the corresponding propargylamines. Two tandem reactions, including an additional cyclization step, leads to the effective production of indoles and imidazopyridines. In particular, the lamellar compound [Cu(BDC)] (BDC = benzene dicarboxylate) is highly efficient for the preparation of imidazopyridines, although a progressive structural change of the solid to a catalytically inactive compact structure is produced, causing deactivation of the catalyst. Nevertheless, the phase change can be reverted by refluxing in DMF, which recovers the original lamellar structure and the catalytic activity of the fresh material. The use of [Cu(BDC)] for this reaction also prevents the formation of Glaser/Hay condensation products of the alkyne, even when the reaction is performed in air atmosphere. This is a further advantage of [Cu(BDC)] with respect to other homogeneous copper catalysts, for which the use of an inert atmosphere is necessary. (C) 2011 Elsevier Inc. All rights reserved.