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The Explicit Theory of “Real” Electrocyclizations of Closed and Open Shell Molecules

  • Nicolaos Demetrios Epiotis
Part of the Lecture Notes in Chemistry book series (LNC, volume 34)

Abstract

The purpose of this chapter is threefold:
  1. a.

    To develop the explicit theory of pericyclic reactions by reference to the electrocyclization reaction in a way that makes new analogies possible.

     
  2. b.

    To show that the stereoselection rules for model and “real” closed shell electrocyclizations are identical.

     
  3. c.

    To show that the stereoselection rules for model radical electrocyclizations are opposite to those for “real” radical electrocyclizations because these reactions are not simple “n electrons in n pi AO’s” reactions but, rather, sigma-pi transfer reactions of the type that current qualitative theory cannot deal with in a formally satisfactory and conceptually intelligible way. The MOVB theory of stereoselection of “real” radical electrocyclic reactions destroys the impasse which has been reached in the field of radical chemistry with regards to the stereoselectivity of radical reactions, in general.

     

Keywords

Interaction Matrix Element Ligand Orbital Sigma Bond Pericyclic Reaction Fragment Orbital 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. 1.
    Epiotis, N.D., Larson, J.R., Eaton, H., “Unified Valence Bond Theory of Electronic Structure” in Lecture Notes in Chemistry, Vol. 29; Springer-Verlag: New York and Berlin, 1982.Google Scholar
  2. 2.
    Woodward, R.B., Hoffmann, R., J. Am. Chem. Soc. 1965, 87, 395.CrossRefGoogle Scholar
  3. (a).
    Longuet-Higgins, H.E.; Abrahamson, E. J. Am. Chem. Soc. 1965, 87, 2045.CrossRefGoogle Scholar
  4. (b).
    Hoffmann, R., Woodward, R.B., J. Am. Chem. Soc. 1965, 87, 2046.Google Scholar
  5. 4.
    These are constructed using the philosophy of the United Atom method.Google Scholar
  6. 5.
    For review, see: Epiotis, N.D., Shaik, S., Zander, W., “Rearrangements: A Theoretical Approach” in “Rearrangements in Ground and Excited States”, de Mayo, P., Ed., Vol. 2; Academic Press: New York, 1980.Google Scholar
  7. 6.
    Marvell, E.N., “Thermal Electrocyclic Reactions”; Academic Press: New York, 1980.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1983

Authors and Affiliations

  • Nicolaos Demetrios Epiotis
    • 1
  1. 1.Department of ChemistryUniversity of WashingtonSeattleUSA

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