Dipolar cycloadditions and the “|Δμ| big is good” rule: a computational study

We analyze the validity of the “|Δμ| big is good” rule over a set of different 1,3-dipolar cycloaddition reactions. We consider different factors that could be important in the practical application of this principle, chiefly: intermolecular interactions and geometry reorganization. We observe that while a simple model of the reagent–reagent perturbations suffices to describe charge transfer in these reactions, it fails when applied to the “|Δμ| big is good” rule. On the contrary, geometry changes are proven to be of paramount importance and only when they are correctly taken care of the “|Δμ| big is good” rule provides accurate predictions.