Diradical-singlet character of 1,3-dipoles affects reactivity of 1,3-dipolar cycloaddition reactions and intramolecular cyclization

1,3-Dipolar cycloaddition (1,3-DC) reactions are powerful synthetic tool to obtain highly functionalized 5-membered heterocycles, starting from a 1,3-dipole and a dipolarophile in a single step. The reactivity of these systems is usually rationalized in terms of Frontier Molecular Orbital Theory (FMOT), which neglects a possible contribution of an open-shell weakly coupled singlet-diradical specie. In this work, the broken-symmetry approach is used to estimate the singlet-diradical character of 18 dipoles of the second period of the periodic table, classified as allyl-type N-centered, allyl-type O-centered, and propargyl-type 1,3-dipoles, providing a rationalization for 1,3-DC reactivity. The intramolecular cyclization of bent allyl-type N- and O-centered dipoles into 3-membered rings was also analyzed, and revealed that the energetic change is associated with the spin densities of peripheral atoms. Finally, a close relationship between the energy for the ring-opening process of the cyclic configuration and the reactivity of 1,3-dipoles toward 1,3-dipolar cycloaddition reaction was also found.