The present work reports the theoretical study of the reaction between anthrones and maleimides organocatalyzed by bifunctional thiourea. It has been observed that the substituents attached to the reactant determine the reaction path, which in turn induces the formation of different products. Our mechanistic study has explored the various possible routes for the product formation. We observed that the non-covalent interactions specifically the N–H⋯O and C–H⋯O play a decisive role in deciding the fate of stereoselectivity of the products. The formation of favoured/disfavoured products is accounted on the basis of energy profiling. The reaction results in outstanding yields and enantioselectivities of Diels–Alder cycloadduct when N-phenylmaleimide is used as dienophile (99% ee, RR configuration), whereas Michael adduct is formed as a major product on using N-(4-trifluoromethylphenyl)maleimide (99% ee, S configuration). These theoretically obtained results are in line with the experimentally observed values. The difference in the reactant stimulates the variation in the interactions, and these insights can eventually aid the experimentalists to design subsequent experiments in the future.