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For polar Diels–Alder (DA) reactions, one of the most relevant aspects is its dependence on the reaction media; thus, in this work, the objective is to analyze the effect of aqueous micellar systems on the synthesis of compounds of biological interest. Based on the system formed by isoprene and 2-nitrofuran, the experiments were carried out in micellar media formed by amphiphilic ionic liquid (<i>N</i>,<i>N</i>-dodecylmethylimidazolium bromide) and by conventional surfactants (SDS and CTAB). In this sense, there are few studies that involve DA reactions in micro-heterogeneous systems. The challenge is to have the knowledge about the behavior of ILs in order to take advantage of all their potentialities in order to replace a toxic molecular solvent with ILs, which allows the development of a methodology framed within the concepts of Green Chemistry.