An environmentally friendly and economically favorable approach to the formation of C-N bonds is presented. The methodology is particularly interesting in that the reaction is realized under both solvent-and ligand-free conditions and involves the use of a low loading of a palladium catalyst dispersed with the reactants on a suitable solid support. The reaction proceeds rapidly under microwave irradiation.The formation of C-N bonds is an important operation in organic synthesis, and transition-metal-catalyzed reactions are useful tools for preparing a wide range of nitrogen-containing compounds. 1 Despite the considerable efforts that have been made to develop new procedures in this field, only a small percentage of fine chemicals are produced by using homogeneous catalysis, probably as a result of several critical factors, such as the availability, cost, activity, and stability of catalysts and compatibility matching of starting materials. Arylamines are building blocks that are widely used in the synthesis of a variety of compounds, including pharmaceutical intermediates, agrochemicals, dyes, and polymers. 2 Among palladium-catalyzed amination processes, the Buchwald-Hartwig reaction represents a useful strategy for preparing substituted arylamines. 3 Since the initial reports on the reaction in 1995, 4 much attention has been directed to clarifying how the outcome of the BuchwaldHartwig reaction is influenced by the choice of the palladium precatalyst, the base, and, above all, the ligands, which accelerate the oxidative addition and enhance the reductive elimination. 5 Also the ability of ligands to stabilize palladium(0)-species, to prevent palladium agglomeration, and to maintain catalytic properties ensures that they play a major role in the reaction. The literature reports the use of various combinations of a palladium compound, such as palladium(II) acetate, bis(dibenzylideneacetone)palladium, or tris(dibenzylideneacetone)dipalladium, with a range of phosphine ligands, such as 1,1′-binaphthalene-2,2′-diylbis(diphenylphosphine) (BINAP) or 1,1′-bis(diphenylphosphinyl)ferrocene (DPPF), tritert-butylphosphine, or biaryl(dialkyl)phosphines. 6 However, the use of ligands has some drawbacks resulting from their sensitivity to water or air. Moreover, ligands cannot normally be recovered after the reaction and their presence frequently hampers the isolation and purification of the desired product. Finally, ligands are often more expensive than catalysts and not easily available. In attempts to overcome these drawbacks, several phosphine-free systems have been investigated; these show excellent activities in many typical palladium-catalyzed procedures, such as Heck reactions and arylation reactions 7,8 or carbonylation processes. 9 Recently, ligandfree palladium-catalyzed C-S bond-formation reactions have been reported in the literature, 10 and, very recently, studies on the Buchwald-Hartwig process have been reported. 11 Moreover, successful ligand-free approaches to copper-catalyzed amination reactions have also...