in preparative scale [e.g. 3.30 g of N-(1,3-diphenylallyl)-4-nitroaniline]. The catalyst could be reused up to 15 cycles without loss of activity, proving its robustness.

A metal-organic framework (MOF) based on copper and 1,3-bis(carboxymethyl)imidazole [Cu(bcmim)2] has been prepared up to gram-scale, using a precipitation methodology at room temperature. The MOF-Cu(bcmim)2 has proved to be a very efficient catalyst in the preparation of amides via an oxidative coupling between carboxylic acids and formamides in the presence of an oxidant, such as TBHP. The methodology for the preparation of amides has shown to be very robust regardless of the carboxylic acid, giving good conversions and selectivities. The heterogeneous catalyst has been recovered unaltered after the reaction, being easily separated from the reaction mixture and subsequently reactivated by suitable treatment. Moreover, the coupling reaction has been scaled up to gram-scale, being possible to prepare valuable products, such as fatty acid amides (i.e. 1-palmitoylpiperidine).

Quinoline and acridine derivatives have been prepared using a functionalized imidazolium salt as heterogeneous catalyst. Different ketones have been coupled with 2‐aminobenzaldehydes and 2‐aminoaryl ketones under solvent‐free conditions, employing 1,3‐bis(carboxymethyl)‐imidazolium chloride as a catalyst. The protocol is simple and effective for the synthesis of a variety of nitrogen containing heterocycles (> 35 examples) with moderate to excellent yields (up to 96 %), being possible to perform the reaction in preparative scale. Additionally, 3‐acetylquinolines have been transformed, under solvent‐free conditions, into quinolyl chalcone derivatives by means of the same catalyst. Thus, the catalytic system mediates both reactions effectively in a tandem procedure. Furthermore, the catalyst is easily separated from the reaction mixture and can be reused without loss of activity (up to 8 cycles) which remarks its sturdiness. The E‐factors are in the range of 14–23, both for the formation of quinolines and for the tandem reaction, which demonstrates the sustainability of the protocols described.

This article details the development of heterogeneous catalysts based on calcium and barium in combination with the organic linker 1,3‐bis(carboxymethyl)imidazolium (bcmim). The linker and the materials from alkaline earth metals are easily prepared under very smooth conditions. The use of linkers with different counterions (Cl or Br) provided different materials. Calcium‐ and barium‐based catalysts were successfully employed in the preparation of quinoline derivatives from ketones and 2‐aminoarylaldehydes or 2‐aminoarylketones. In general, barium‐based catalysts provided better results than calcium, although the latter are an excellent complement for certain substrates. Thus, a notable feature of such catalysts is the possibility of accessing a variety of complementary heterogeneous catalytic systems, rendering the catalysis adaptive to the reactant.||||||

Metal‐free catalysts based on 1,3‐bis(carboxymethyl)imidazolium halides mediate the reaction between allylic alcohols and anilines, providing the corresponding N‐, 2‐ and 4‐allylaniline isomers selectively. The imidazolium counterion plays a crucial role in the outcome of the reaction. Thus, while the imidazolium chloride selectively provides the N‐substituted aniline, the bromide and iodide imidazolium salts produce the 2‐ and 4‐allylaniline isomers, respectively, with excellent selectivities. A set of complementary catalysts, which are available by simple modulation, is here presented to conduct a highly regioselective allylation reaction of anilines. Not only the catalysts are synthesized in a straightforward and easily scalable manner, but they can be recycled and used under solvent‐free reaction condition, due to the favorable interactions with the reactants.