Structural Chemistry

, Volume 7, Issue 1, pp 73–77 | Cite as

Rearrangement of a trishomocubane derivative to a tetracyclo[6.3.0.02,6.03,10]undec-4-ene

  • Alexander M. Aleksandrov
  • Mariusz Krawiec
  • Tonis J. Pehk
  • Alexander Petrenko
  • William H. Watson
Article
  • 21 Downloads

Abstract

Reaction of 8,8,11,11-tetrafluoropentacyclo[5.4.0.02,6.03,10.05,9]undecane with idio trimethylsilane leads to the expectedd3-trishomocubane derivative, but reaction with the more electrophilic boron tribromide yields a tetracyclo[6.3.0.02,6.03,10]undec-4-ene derivative which was characterized by X-ray diffraction. The most easily visualized pathway for this transformation would be an initial rearrangement of the starting material to ad3-trishomocubane followed by additional bond breaking to form the undec-4-ene compound. Molecular mechanics calculations indicate the brominatedd3-trishomocubane is about 4 kcal/mol more stable than the brominated undec-4-ene molecule and the associated carbonium ions show the same ordering. These data would indicate an alternate reaction pathway must be operative; however, semiempirical calculations predict the reverse ordering of the above energies.

Key words

Tetracycloundecane d3-trishomocubane tetracycloundec-4-ene molecular mechanics semiempirical calculations X-ray analysis carbonium ion rearrangements 

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Copyright information

© Plenum Publishing Corporation 1996

Authors and Affiliations

  • Alexander M. Aleksandrov
    • 1
  • Mariusz Krawiec
    • 3
  • Tonis J. Pehk
    • 2
  • Alexander Petrenko
    • 1
  • William H. Watson
    • 3
  1. 1.Institute of Bioorganic ChemistryUkrainian Academy of SciencesKievUkraine
  2. 2.Institute of Chemical and Biological PhysicsEstonian Academy of SciencesTallinnEstonia
  3. 3.Department of ChemistryTexas Christian UniversityFort Worth

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