Structural Chemistry

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

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

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


Reaction of 8,8,11,11-tetrafluoropentacyclo[,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[,6.03,10]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 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Marchand, A. P. InAdvances in Theoretically Interesting Molecules; Thummel, R. P., Ed.; JAI: Greenwich, CT, 1989; Vol. 1, pp 357.Google Scholar
  2. 2.
    Marchand, A. P.Chem. Rev.,1989,89, 1011.Google Scholar
  3. 3.
    Alexandrov, A. M.; Sorochinskii, A. E.; Petrenko, A. E.; Kukhar, V. P.J. Org. Chem. (USSR) (Engl. Transl.)1987,23, 681.Google Scholar
  4. 5.
    Sheldrick, G. M.SHELXS86 1986.Program for the solution of crystal structures; Univ. of Göttingen, Germany.Google Scholar
  5. 6.
    TEXSAN1985,TEXRAY Structure Analysis Package. Molecular Structure Corporation, The Woodlands, TX.Google Scholar
  6. 7.
    Spek, A. L.Acta Cryst. 1990,A46, C43.Google Scholar
  7. 8.
    Cremer, D.; Pople, J. A.J. Am. Chem. Soc. 1975,97, 1354.Google Scholar
  8. 9.
    Watson, W. H.; Kashyap, R. P.; Krawiec, M.; Marchand, A. P.; Tsay, F.-R.Struct. Chem. 1994,5, 21.Google Scholar
  9. 10.
    PCMODEL. Molecular Modeling Software 1994. Serena Software, Bloomington, IN.Google Scholar
  10. 11.
    Allinger, N. L.; Yuh, Y. H.; Lii, J.-H.J. Am. Chem. Soc. 1989,111, 8551–8566. MM3 program from Technical Utilization Corporation, Powell, OH, Update Jan. 1990.Google Scholar
  11. 12.
    MOPAC 6.00 1993. QCPE 455.Google Scholar
  12. 13.
    Hamilton, W. C.Acta Crystallogr. 1965,18, 502.Google Scholar

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

Personalised recommendations