The diastereoselective cycloadditions of enantiopure nitrilimines 4 with ethyl acrylate were exploited in dry toluene and in aqueous sodium hydrogencarbonate as reaction media. Shorter reaction times and improved diastereoisomeric ratios of the resulting 5-ethoxycarbonyl-4,5-dihydropyrazoles 5 and 6 were observed in aqueous media.