The pseudo-intramolecular Diels−Alder (DA) reaction between a 2-substituted furan (1) and a N-maleimidederivative (2) has been analyzed using DFT methods. Formation of two hydrogen bonds between theappendages on furan and maleimide derivatives favors thermodynamically the formation of a molecularcomplex (MC1) through an efficient molecular recognition process. The large enthalpy stabilizationassociated with the molecular recognition overcomes the unfavorable activation entropy associated withthe bimolecular process. As a consequence, the subsequent DA reaction is clearly accelerated through apseudo-intramolecular process.