C–H⋯π interactions as modulators of carbocation structure – implications for terpene biosynthesis

Abstract

Density functional theory calculations on geometries and interaction energies for C–H⋯π interactions involving carbocations are described. C–H bonds involved in strong hyperconjugation are shown to be strong C–H⋯π donors and their participation in C–H⋯π interactions with specific geometries is shown to promote large modifications to the structures of carbocations. Implications for terpene biosynthesis are discussed.