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Related Experiment Videos

The cationic cascade route to longifolene.

Gregory A Ho1, Dustin H Nouri, Dean J Tantillo

  • 1Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA.

The Journal of Organic Chemistry
|June 18, 2005
PubMed
Summary

W. S. Johnson's classic longifolene synthesis is revisited using computational chemistry. Hybrid Hartree-Fock/density functional theory calculations validate the proposed cationic polycyclization mechanism for this complex molecule.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Quantum Chemistry

Background:

  • W. S. Johnson's total synthesis of longifolene is a landmark achievement in organic chemistry.
  • The synthesis prominently features a cationic polycyclization cascade for constructing the complex sesquiterpenoid framework.

Purpose of the Study:

  • To computationally investigate and validate the key cationic polycyclization step in Johnson's longifolene synthesis.
  • To explore the electronic properties of a key intermediate and the impact of structural modifications on its bonding.

Main Methods:

  • Hybrid Hartree-Fock/density functional theory (HF/DFT) calculations were employed.
  • Analysis focused on the mechanism of the cationic polycyclization and the nature of 3-center 2-electron bonding in intermediates.

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Main Results:

  • The computational study provides strong support for the feasibility of Johnson's proposed polycyclization mechanism.
  • Perturbations to the polycyclic framework significantly alter the 3-center 2-electron bonding array in a critical intermediate.

Conclusions:

  • The study validates the mechanistic pathway of a pivotal reaction in a classic natural product synthesis using modern computational tools.
  • Understanding the electronic structure of intermediates offers insights into the design principles for complex molecule construction via polycyclization.