Hyperconjugation enhances electrophilic addition to monocyclic monoterpenes: a Fukui function perspective.

The local and condensed Fukui functions as well as the principle of hard and soft acids and bases were used to study the addition of free radicals to the exocyclic and endocyclic double bonds of seven monocyclic monoterpenes of formula C10H16. The results obtained showed that, in general, the most reactive double bond was the one with the most substituents on the double-bonded carbon atoms, and that the reaction of a double bond with an electrophile is a soft-soft interaction. The effects of substituents on the double-bonded carbon atoms and the stabilization of the monoterpenes were interpreted by invoking hyperconjugated structures, which led us to propose a simple rule: the larger the value of the Fukui function for the double bond, the greater the hyperconjugative stabilization and the susceptibility of the double bond to electrophilic attack. In general, our results are in good accordance with relevant experimental and theoretical results published in the literature. Graphical abstract The specific electrophilic addition to monocyclic monoterpenes.