The cationic cascade route to longifolene.
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.
Ho
Gregory A
GA
Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA.
Nouri
Dustin H
DH
Tantillo
Dean J
DJ
D002384:Catalysis; D003500:Cyclization; D007202:Indicators and Reagents; D008968:Molecular Conformation; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis*
D007202:Indicators and Reagents; D012717:Sesquiterpenes; C035607:longifolene