title: The cationic cascade route to longifolene.
abstract: W. S. Johnson's total synthesis of the sesquiterpenoid longifolene is a classic example of the power of cationic polycyclizations for constructing complex molecular architectures. Herein we revisit the key polycyclization step of this synthesis using hybrid Hartree-Fock/density functional theory calculations and validate the feasibility of Johnson's proposed mechanism. We also explore perturbations to the 3-center 2-electron bonding array in a key intermediate that result from changing the polycyclic framework in which it is embedded.
authors.affiliation: Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA.
authors.forename: Gregory A
authors.initials: GA
authors.lastname: Ho
authors.forename: Dustin H
authors.initials: DH
authors.lastname: Nouri
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
mesh_terms: D002384:Catalysis; D003500:Cyclization; D007202:Indicators and Reagents; D008968:Molecular Conformation; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis*
chemical_list: D007202:Indicators and Reagents; D012717:Sesquiterpenes; C035607:longifolene