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DOI: 10.1039/A702435E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 1955-1958

Hexacyclo[8.7.0.03,8.05,15.06,13.012,16]heptadeca-1(10),5-diene-3,8-dicarboxylic anhydride, a tetrahydro[4]beltene with two σ-conjugated double bonds

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Wolfram Grimme, Heinz Geich, Johann Lex and Jürgen Heinze

Abstract

The tetrahydro[4]beltene 8 has been synthesized via a sequence of three Diels–Alder reactions. As shown in the crystal structure of 8, the two double bonds in the cage diene are positioned face-to-face at a distance of 2.92 Å, which is smaller than the sum of their van der Waals radii. The resulting σ-conjugation in 8 is evident from the long wavelength UV adsorption and from the formation of a stable radical cation at low potential. Hydrogenation increases the strain of 8 such that only one double bond can be saturated under forcing conditions.

References

  1. O. Ermer, Aspekte von Kraftfeldrechnungen, W. Bauer Verlag, München, 1981, pp. 311–312 Search PubMed.
  2. R. W. Alder and R. B. Sessions, J. Chem. Soc., Perkin Trans. 2, 1985, 1849 RSC.
  3. P. R. Ashton, N. S. Isaacs, F. H. Kohnke, A. M. Z. Slawin, C. M. Spencer, J. F. Stoddart and D. J. Williams, Angew. Chem., 1988, 100, 981 CAS; Angew. Chem., Int. Ed. Engl., 1988, 27, 966 Search PubMed; P. R. Ashton, N. S. Isaacs, F. H. Kohnke, J. P. Mathias and J. F. Stoddart, Angew. Chem., 1989, 101, 1266 Search PubMed; Angew. Chem., Int. Ed. Engl., 1989, 28, 1258 CAS; F. H. Kohnke, J. P. Mathias and J. F. Stoddart, Top. Curr. Chem., 1993, 165, 1 CAS; A. Godt, V. Enkelmann and A.-D. Schlüter, Angew. Chem., 1989, 101, 1704 Search PubMed; Angew. Chem., Int. Ed. Engl., 1989, 28, 1680 CAS; J. Benkhoff, R. Boese, F.-G. Klärner and A. E. Wigger, Tetrahedron Lett., 1994, 35, 73 CAS.
  4. W.-D. Fessner, B. A. R. C. Murty, P. R. Spurr, R. Pinkos, J.-P. Melder, H. Fritz and H. Prinzbach, Chem. Ber., 1992, 125, 1697 CAS.
  5. MM2 +π-VESCF routine MMP1 (both from N. L. Allinger) as contained in PCMODEL, Serena Software, Bloomington, IN.
  6. W. R. Roth, H. Humbert, G. Wagner, G. Erker and H.-D. Exner, Chem. Ber., 1975, 108, 1655 CAS; W.-D. Fessner, B. A. R. C. Murty and H. Prinzbach, Angew. Chem., Int. Ed. Engl., 1987, 26, 451 CrossRef.
  7. This seemingly simple strategy is not free of problems, as shown by R. W. Alder, P. R. Allen, L. S. Edwards, G. I. Fray, K. E. Fuller, P. M. Gore, N. M. Hext, A. R. Thomas and K. S. Turner, J. Chem. Soc., Perkin Trans. 1, 1994, 3071 Search PubMed.
  8. H. Geich, W. Grimme and K. Proske, J. Am. Chem. Soc., 1992, 114, 1492 CrossRef CAS.
  9. Dyotropic hydrogen transfers that aromatize cyclohexadienes are highly exothermal and symmetry allowed. Best studied is the (2π+ 4σ)-version of this reaction which proceeds in an inter- as well as an intra-molecular fashion. W. von E. Doering and J. W. Rosenthal, J. Am. Chem. Soc., 1967, 89, 4535, K. Mackenzie, J. Chem. Soc., 1965, 4646 Search PubMed; K. Mackenzie, G. Proctor and D. J. Woodnutt, Tetrahedron, 1987, 43, 5981 Search PubMed; K. Mackenzie, J. A. K. Howard, R. Siedlecka, K. B. Astin, E. C. Gravett, C. Wilson, J. Cole, R. G. Gregory and A. S. Tomlins, J. Chem. Soc., Perkin Trans. 2, 1996, 1749 CrossRef CAS.
  10. H. Prinzbach, B. A. R. C. Murty, W.-D. Fessner, J. Mortensen, J. Heinze, G. Gescheidt and F. Gerson, Angew. Chem., 1987, 99, 488 CAS; Angew. Chem., Int. Ed. Engl., 1987, 26, 457 Search PubMed; T. Bally, Chimia, 1994, 48, 378 Search PubMed.
  11. G. Gescheidt, R. Herges, H. Neumann, J. Heinze, M. Wollenweber, M. Etzkorn and H. Prinzbach, Angew. Chem., 1995, 107, 1109; Angew. Chem., Int. Ed. Engl., 1995, 34, 1016 Search PubMed.
  12. W. F. Maier and P. v. R. Schleyer, J. Am. Chem. Soc., 1981, 103, 1891 CrossRef CAS.
  13. M. A. P. Bowe, R. G. J. Miller, J. B. Rose and D. G. M. Wood, J. Chem. Soc., 1960, 1541 RSC.
  14. Y. A. Slobodin and A. P. Khitrov, Zh. Obshch. Khim., 1963, 33, 2819 CAS.
  15. MolEN is an interactive structure solution procedure, Nonius, Delft, The Netherlands.
  16. SHELXL-93: Program for the refinement of crystal structures by G. M. Sheldrick, University of Göttingen, Germany, 1993.
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