The cationic cascade route to longifolene

J Org Chem. 2005 Jun 24;70(13):5139-43. doi: 10.1021/jo0503658.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cyclization
  • Indicators and Reagents
  • Molecular Conformation
  • Molecular Structure
  • Sesquiterpenes / chemical synthesis*

Substances

  • Indicators and Reagents
  • Sesquiterpenes
  • longifolene