1.
J Org Chem
; 70(13): 5139-43, 2005 Jun 24.
Artículo
en Inglés
| MEDLINE
| ID: mdl-15960516
RESUMEN
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.