Understanding the mechanism of non-polar Diels–Alder reactions. A comparative ELF analysis of concerted and stepwise diradical mechanisms

The electron-reorganization along the concerted and stepwise pathways associated with the non-polar Diels–Alder reaction between cyclopentadiene (Cp, 1) and ethylene (2) has been studied using the topological analysis of the electron localization function (ELF) at the B3LYP/6-31G(d) level of theory. ELF results for the concerted mechanism stresses that the electron-reorganization demanded on the diene and ethylene reagents to reach two pseudo-diradical structures is responsible for the high activation energy. A comparative ELF analysis of some relevant points of the non-polar Diels–Alder reaction between Cp and styrene (10) suggests that these concerted mechanisms do not have a pericyclic electron-reorganization.