In this work we studied the capability of several diene/dienophile pairs to undergo Diels-Alder (DA) reactions leading to benzo[b]thiophenes. A variety of synthetically and commercially available nitrothiophenes were chosen as dienophiles. Methyl 5-nitro-3-thiophenecarboxylate was selected as a potential strong electrophilic candidate based on some DFT-based properties and the substitution pattern of the expected product. The mechanistic details concerning the participation of this dienophile in polar DA reactions were investigated through a theoretical point of view. The results were compared with the experimental outcomes. This methodology should allow synthetic chemists to analyze DA reactions in detail in a stage prior to the synthetic job.Fil: Brasca, Romina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral; ArgentinaFil: Kneeteman, Maria Nelida. Universidad Nacional del Litoral; ArgentinaFil: Mancini, Pedro Maximo Emilio. Universidad Nacional del Litoral; ArgentinaFil: Fabian, Walter M.F.. Karl-franzens-universitat Graz; Austria