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Related Experiment Videos

Facile 1,3- and 1,5-Chlorine Migration.

Rainer Koch1, Ming Wah Wong, Curt Wentrup

  • 1Department of Chemistry, The University of Queensland, Brisbane, Queensland 4072, Australia.

The Journal of Organic Chemistry
|October 4, 1996
PubMed
Summary

Chlorine migration is dramatically accelerated by lone pair-lowest unoccupied molecular orbital (LUMO) interactions, enabling pericyclic reactions. This mechanism significantly lowers activation barriers compared to unassisted shifts.

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Area of Science:

  • Computational Chemistry
  • Organic Reaction Mechanisms
  • Quantum Chemistry

Background:

  • Chlorine migration reactions are fundamental in organic chemistry.
  • Understanding the factors influencing chlorine shift barriers is crucial for predicting reactivity.
  • Previous studies on sigmatropic shifts often focused on unassisted mechanisms.

Purpose of the Study:

  • To investigate the mechanism of 1,3- and 1,5-chlorine migrations using computational methods.
  • To explore the role of orbital interactions in accelerating chlorine shifts.
  • To compare activation barriers of assisted versus unassisted chlorine migrations.

Main Methods:

  • High-level ab initio molecular orbital calculations (G2(MP2,SVP) theory).
  • Semiempirical methods were also employed for comparison.

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  • Analysis of transition structures to determine migration pathways and orbital interactions.

    • Main Results:

    • Lone pair-lowest unoccupied molecular orbital (LUMO) interaction dramatically accelerates chlorine shifts via pericyclic reactions.
    • Significantly reduced activation barriers observed for chloro oxo ketene and (2-(chlorocarbonyl)vinyl)ketene compared to unassisted shifts.
    • Chlorine migration occurs within the molecular plane in studied systems.

    Conclusions:

    • The lone pair-LUMO-mediated mechanism is a key factor in accelerating 1,3- and 1,5-chlorine migrations.
    • This mechanism offers a substantial reduction in activation energy compared to conventional sigmatropic shifts.
    • Orbital interactions play a critical role in the feasibility and rate of these chlorine migration reactions.