title: Dynamic behavior of rearranging carbocations - implications for terpene biosynthesis.
abstract: This review describes unexpected dynamical behaviors of rearranging carbocations and the modern computational methods used to elucidate these aspects of reaction mechanisms. Unique potential energy surface topologies associated with these rearrangements have been discovered in recent years that are not only of fundamental interest, but also provide insight into the way Nature manipulates chemical space to accomplish specific chemical transformations. Cautions for analyzing both experimental and theoretical data on carbocation rearrangements are included throughout.
authors.affiliation: Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, CA 95616, USA.
authors.forename: Stephanie R
authors.initials: SR
authors.lastname: Hare
authors.affiliation: Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, CA 95616, USA.
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
keywords: carbocation; density functional theory; dynamics; mechanism; terpene