1,3-dipolar cycloaddition reactions of an electron deficient C-aryl-N-phenyl nitrone to benzylidene derivatives (with different electrophilicities) have been analyzed by density functional theory calculations. The transition states corresponding to the endo and exo approaches along the feasible regioisomeric reaction channels have been located for each cycloaddition. The reactions follow a concerted mechanism with asynchronous transition states. The asynchronicity along the regiochemical reaction modes depends on the β-carbon electrophilicities of the olefins. The regio and stereochemistries predicted from the calculated activation energy barriers (with solvent and higher basis set corrections) of the located transition states are in conformity with the experimental results. The local electrophilicities, softness matching indices and the interaction energies were then calculated to analyze how well these reactivity parameters can interpret the regioselectivities of such reactions. The electronic populations at the reactive sites computed from electrostatic potential-driven atomic charges provided correct and consistent predictions for each theoretical model contrary to the natural orbital based charges.