Understanding the polar mechanism of the ene reaction. A DFT study

The molecular mechanism of ene reactions has been characterised by DFT methods at the MPWB1K/6-311G(d,p) level of theory. Most reactions take place along a two-stage one-step mechanism in which the C-C bond formation takes place before the hydrogen transfer process. A very good correlation between the polar character of the reaction measured by the global electron density transfer at the transition state and the activation energy has been found. This behaviour allows establishing a useful classification of ene reactions in N-ene having a very high activation energy, P-ene reactions having activation energies between 35 and 20 kcal mol^-1, and H-ene reactions having activation energies below 20 kcal mol^-1. ELF topological analysis allows the characterisation of the two-stage one-step mechanism associated with a two-centre nucleophilic/electrophilic interaction. Formation of the C-C single bond is achieved by the C-to-C coupling of two pseudoradical centres formed at the two interacting carbon atoms in the first stage of the reaction. This topological analysis establishes that bonding changes are non-concerted. Finally, a DFT reactivity analysis makes it possible to characterise the electrophilic/nucleophilic behaviour of the reagents involved in ene reactions, and consequently, to predict the feasibility of ene reactions.