Understanding the mechanisms of [3+2] cycloaddition reactions. The pseudoradical versus the zwitterionic mechanism

Analysis of 12 three-atom-components (TACs) participating in [3+2] cycloaddition (32CA) reactions towards ethylene and acetylene allows establishing good correlations between the pseudodiradical character, the hardness η, and the nucleophilicity N index of the TAC with the feasibility of these non-polar reaction. These results allow the introduction of the pr index, which comprises the two aforementioned DFT reactivity indices. The increase of the pr index for an allylic-type TAC goes accompanied by a linear decrease of the activation enthalpy of the reaction. The present study makes it possible to establish a useful classification of 32CA reactions into zw-type reactions involving TACs with a high zwitterionic character, and pr-type reactions involving TACs with a high pseudodiradical character.