Electrostatic origin towards the reversal of π-facial selectivity of 5,6-cis,exo-disubstituted bicyclic[2.2.2]oct-2-enes with m-chloroperbenzoic acid and diazomethane: a computational study

A computational (B3LYP/6-31G∗ and MP2/6-31G∗) study shows that electrostatic interaction is controlling the π-facial selectivity for the addition of peracid and diazomethane to 5,6-cis,exo-disubstituted bicyclic[2.2.2]oct-2-enes (1). The nitrogen centre of diazomethane which does not participate in bond formation governs the π-face selectivity in 1,3-dipolar cycloaddition reactions with 1. The calculated results show that Cieplak model is less important in controlling the face selectivity in these cases.