CHEMICAL REPERCUSSIONS OF ORBITAL INTERACTIONS THROUGH BOND AND THROUGH SPACE. THE REACTIVITY OF THE DOUBLE BOND IN UNSATURATED CYCLIC SULPHONES TOWARDS AZIRIDINE FORMATION AND EPOXIDATION

Article abstract of DOI:10.1016/S0040-4020(01)83501-8

The ease of formation of aziridine and/or epoxides from a series of bicyclic olefins, where distant sulphonyl groups are present, is very variable.There is some correlation between reactivity of the vinyl group and its ?-ionisation potential which is high in the present molecules relative to comperison olefins.This increase is thought to be due to the presence of orbital interactions through bonds and/or through space between the sulphone group and the double bond, making the latter electron deficient.The ionisations potentials were determined by UV-photoelectron spectroscopy and the assignments made by recourse to ab initio configuration interaction methods.