title: Successful computational modeling of isobornyl chloride ion-pair mechanisms.
abstract: Along with the directly related Wagner-Meerwein camphene hydrochloride-isobornyl chloride rearrangement, the racemization of isobornyl chloride involves intermediate carbocation-anion ion pairs; both processes have become mechanistic icons in organic chemistry. The two known racemization pathways, involving either a hydride transfer or a methyl migration, are observed to be concurrent. However, prior quantitative computational modeling has not been able to reproduce the fine kinetic balance of these processes. We demonstrate that a density functional approach, which includes two explicit solvent molecules embedded in a continuum solvent field, coupled with full geometric optimization using smoothed solvent cavities and free energy calculation, yields results in accord with experiment. Alternative racemization routes also have been explored.
authors.affiliation: Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China.
authors.forename: Jing
authors.initials: J
authors.lastname: Kong
authors.forename: Paul v R
authors.initials: Pv
authors.lastname: Schleyer
authors.forename: Henry S
authors.initials: HS
authors.lastname: Rzepa