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Thermodynamic vs. kinetic control in the Diels-Alder cycloaddition of cyclopentadiene to 2,3-dicyano-p-benzoquinone

Abstract

Diels-Alder cycloaddition of cyclopentadiene (1a) to 2,3-dicyano-p-benzoquinone (2a), when performed in methanol solvent at ambient temperature, proceeds with kinetic control to afford 1α,4α,4aβ,8aβ-tetrahydro-5,8-dioxo-1,4-methanonaphthalene-4a,8a-dicarbonitrile (7, 77% yield). However, when this cycloaddition is performed by refluxing an equimolar solution of1a and2a in benzene for 3 h, the product of thermodynamic control, i.e., 1α,4α,4aα,8aα-tetrahydro-5,8-dioxo-1,4-methanonaphthalene-6,7-dicarbonitrile (3a) is obtained in 64% yield. The structure of3a was confirmed by an analysis of the reduced intramolecular photocyclization product,9.

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References

  1. 1.(a)

    Ungnade, H.E.; McBee, E.T.Chem. Rev. 1958,249.

  2. 1.(b)

    Onishchenko, A.S.Diene Synthesis, S Monson: Jerusalem, 1964, pp 300–303.

  3. 1.(c)

    Flippen-Anderson, J.L.; Gilardi, R.; George, C.; Marchand, A.P.; Jin, P.-W.Acta Crystallogr. 1987, C43, 2151.

  4. 1.(d)

    Linz, G.S.; Zektzer, A.S.; Martin, G.E.; Marchand, A.P.; Jin, P.-W.J. Org. Chem. 1988,53, 2647.

  5. 1.(e)

    Watson, W.H.; Kashyap, R.P.; Marchand, AP.; Lu, S-P.Acta Crystallogr. 1992, C48, 1290.

  6. 1.(f)

    Minter, D.E.; Marchand, A.P.; Lu, S-P.Magn. Reson. Chem. 1992,30, 1132.

  7. 2.(a)

    Mehta, G.M.; Srikrishna, A.; Reddy, A.V.; Nair, M.S.Tetrahedron 1981,37, 4543.

  8. 2.(b)

    Marchand, A.P. InAdvances in Theoretically Interesting Molecules; Thummel, R.P., Ed.; JAI Press: Greenwich, CT; 1989, Vol. 1, pp 357–399.

  9. 2.(c)

    Marchand, A.P.Synlett 1991, 73.

  10. 3.

    SPARTAN, version 3.1; Wavefunction, Inc., 18401 Von Karman, Suite 370, Irvine, CA 92715.

  11. 4.

    Dewar, M.J.S.; Zoebisch, E.G.; Healy, E.F.; Stewart, J.J.P.J. Am. Chem. Soc. 1985,107, 3902.

  12. 5.

    Stewart, J.J.P.J. Comp. Chem. 1989,10, 209.

  13. 6.

    Ansell, M.F.; Nash, B.W.; Wilson, D.A.J. Chem. Soc. 1963, 3028.

  14. 7.

    Perry, G.J.; Sutherland, M.D.Tetrahedron 1982,38, 1471.

  15. 8.

    Mason, M.R.; Smith, J.M.; Bott, S.G.; Barron, A.R.J. Am. Chem. Soc. 1993,115, 4971.

  16. 9.

    Burla, M.C.; Camalli, M.; Cascarano, G.; Giacovazzo, C.; Polidori, G.; Spagna, R.; Viterbo, D.J. Appl. Cryst. 1989,22, 389.

  17. 10.

    Enraf-Nonius.MolEN, An Interactive Structure Solution Procedure; Enraf-Nonius: Delft, The Netherlands. 1990.

  18. 11.

    International Tables for X-ray Crystallography, Vol. IV; Kynoch Press: Birmingham, UK, 1974; pp 99, 149.

  19. 12.

    Pointer, D.J.; Wilford, J.B.; Hodder, O.J.R.J. Chem. Soc. (B) 1971, 2009.

  20. 13.

    Marchand, A.P.; LaRoe, W.D.; Sharma, G.V.M.; Suri, S.C.; Reddy, D.S.J. Org. Chem. 1986,51, 1622, and references cited therein.

  21. 14.

    Johnson, C.K.ORTEPII Report ORNL-5138; Oak Ridge National Laboratory, TN, 1976.

  22. 15.

    Allen, F.H.; Kennard, O.; Watson, D.G.; Brammer, L.; Orpen, A.G.; Taylor, R.J. Chem. Soc., Perkin Trans. II 1987, S1.

  23. 16.

    Ösawa, E.; Kanematsu, K.Molecular Structure and Energetics, Vol. 3; Liebman, J.F.; Greenberg, A., Eds.; VCH: New York; 1986, pp 329–369.

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Bott, S.G., Marchand, A.P. & Kumar, K.A. Thermodynamic vs. kinetic control in the Diels-Alder cycloaddition of cyclopentadiene to 2,3-dicyano-p-benzoquinone. J Chem Crystallogr 26, 281–286 (1996). https://doi.org/10.1007/BF01677782

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Key Words

  • Crystal structure
  • cyclopentadiene
  • 2,3-dicyano-p-benzoquinone
  • Diels-Alder reaction