New compounds with the ethyl hexahydro-1H-pyrrolo[3,2-c]quinoline-2-carboxylate skeleton were prepared by microwave-assisted intramolecular 1,3-dipolar cycloaddition reactions. The reactions were carried out under solvent-free conditions and compared with the same reaction in the presence of a solvent and a catalyst. Steric effects on the selectivity of the reaction were noted and evaluated.