View PDF Version
 
DOI: 10.1039/A807685E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 171-178

Photochemical reaction of bis-aromatic systems: a novel photocycloaddition of pyridine with furan

(Note: The full text of this document is currently only available in the PDF Version )

Masami Sakamoto, Ai Kinbara, Tadao Yagi, Masaki Takahashi, Kentaro Yamaguchi, Takashi Mino, Shoji Watanabe and Tsutomu Fujita

Abstract

The photochemical reaction of the bis-aromatic system pyridine–furan was investigated. Irradiation of a benzene solution containing 3-cyano-2-methoxypyridines 1 (0.02 M) and furan (0.2 M) resulted in the formation of a 1∶1 adduct, 11-cyano-10-methoxy-8-methyl-4-oxa-9-azapentacyclo[5.4.0.02,6.03,11.05,8]undec-9-ene and 10-cyano-9-methoxy-7-methyl-5-oxa-8-azatricyclo[5.4.0.02,6]undeca-3,8,10-triene in 30 and 16% yield, accompanied by the transpositional pyridine, 5-cyano-2-methoxy-6-methylpyridine, and the pyridine dimer, in 2 and 44% yield, respectively, when the reaction conversion reached 48% yield. The cage and the face-to-face structures were established by X-ray structural analyses. The cage adduct was stable under neutral conditions; however, it easily converted to a face-to-face structure in acidic conditions. On the other hand, though the face-to-face structure was stable at rt, the starting pyridine 1 and furan were easily regenerated quantitatively by heating (>100 °C) or irradiation (>290 nm). The 4 + 4 adduct of pyridine with furan was detected by 1H NMR spectroscopy, and subsequently transformed to a cage structure on irradiation.

References

  1. D. Bryce-Smith and A. Gilbert, Tetrahedron, 1976, 32, 1309 CrossRef CAS.
  2. A. Gilbert, Synthetic Organic Photochemistry, ed. W. M. Horspool, Plenum, New York, 1984 Search PubMed.
  3. J. J. McCullough, Chem. Rev., 1987, 87, 811 CrossRef CAS.
  4. J. Fritshe, J. Prakt. Chem., 1867, 101, 333 Search PubMed.
  5. H. Bouas-Laurent, A. Castellan and J.-P. Desvergne, Pure Appl. Chem., 1980, 52, 2633 CAS.
  6. H.-D. Becker, K. Sandros and K. Anderson, Angew. Chem., Int. Ed. Engl., 1983, 22, 495 CrossRef.
  7. C. Kowala, G. Sugowdz, W. H. F. Sasse and J. A. Wunderlich, Tetrahedron Lett., 1972, 4721 CrossRef CAS.
  8. B. K. Seliger and M. Sterns, Chem. Commun., 1969, 978 RSC.
  9. C. Pac, T. Sugioka and H. Sakurai, Chem. Lett., 1972, 39 CAS.
  10. T. Noh and D. Kim, Tetrahedron Lett., 1996, 37, 9329 CrossRef CAS.
  11. K. Mizuno, C. Pac and H. Sakurai, J. Chem. Soc., Perkin Trans. 1, 1974, 2360 RSC.
  12. P. A. Wender, L. Siggel and J. M. Nuss, Organic Photochemistry, ed. A. Padwa, Marcel Dekker, New York and Basel, 1991, vol. 10, p. 357 Search PubMed.
  13. J. Cornelisse, Chem. Rev., 1993, 93, 615 CrossRef CAS.
  14. J. Berridge, D. Bryce-Smith and A. Gilbert, J. Chem. Soc., Chem. Commun., 1974, 964 RSC.
  15. J. C. Berridge, D. Bryce-Smith and A. Gilbert, J. Chem. Soc., Chem. Commun., 1975, 611 Search PubMed.
  16. J. C. Berridge, A. Gilbert and G. N. Taylor, J. Chem. Soc., Perkin Trans. 2, 1980, 2174 Search PubMed.
  17. T. S. Cantrell, J. Org. Chem., 1981, 46, 2674 CrossRef CAS.
  18. A. Gilbert and W. Rodwell, J. Chem. Soc., Perkin Trans. 1, 1990, 931 RSC.
  19. H. Gercia, A. Gilbert and O. Griffiths, J. Chem. Soc., Perkin Trans. 2, 1994, 247 RSC.
  20. The photochemistry of simple and substituted pyridines displaying an isomerization to Dewar pyridine and transpositional pyridines was reported; see (a) K. E. Wilzzbach and D. J. Rausch, J. Am. Chem. Soc., 1970, 92, 2178 CrossRef; (b) Y. Kobayashi, A. Ohsawa and Y. Iitaka, Tetrahedron Lett., 1973, 2643 CrossRef CAS; (c) R. D. Chamber and R. Middleton, J. Chem. Soc., Chem. Commun., 1977, 154 RSC.
  21. Pentafluoropyridine underwent photocycloaddition with ethylene at the C-3–C-4 bond to give a cyclobutane; see M. G. Barlow, D. E. Brown and R. N. Haszeldine, J. Chem. Soc., Chem. Commun., 1977, 669 Search PubMed; J. Chem. Soc., Perkin Trans. 1, 1978, 363 RSC.
  22. M. Sakamoto, M. Kimura, T. Fujita, T. Nishio, I. Iida and S. Watanabe, J. Am. Chem. Soc., 1991, 113, 5859 CrossRef CAS.
  23. M. Sakamoto, M. Takahashi, M. Kimura, M. Fujihira, T. Fujita, I. Iida, T. Nishio and S. Watanabe, J. Org. Chem., 1994, 59, 5117 CrossRef CAS.
  24. M. Sakamoto, T. Sano, M. Takahashi, K. Yamaguchi, T. Fujita and S. Watanabe, Chem. Commun., 1996, 1349 RSC.
  25. International Tables for Crystallography, ed. A. J. C. Wilson, Kluwer Academic Publishers, Dordrecht, Boston and London, 1992, vol. C Search PubMed.
  26. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 221 CrossRef CAS.
  27. The predicted ΔΔE is proportional to (ca1cb1)2+(ca2cb2)2 where cX is the orbital coefficient in the interaction site of the a1–a2 and the b1–b2 bonds using the Salem–Klopman equation (see, for example, I. Fleming, Frontier Orbital and Organic Chemical Reactions, Wiley-Interscience, New York, 1976) Search PubMed.
  28. G. C. Hopkins, J. P. Jonak, H. J. Minnemeyer and H. Tieckelmann, J. Org. Chem., 1967, 32, 4040 CrossRef CAS.
  29. N. M. Chung and H. Tieckelmann, J. Org. Chem., 1970, 35, 2517 CrossRef CAS.
  30. R. P. Mariella and R. Stansfield, J. Am. Chem. Soc., 1951, 73, 1368 CrossRef CAS.
  31. R. P. Mariella, Org. Synth., 1963, Coll. Vol. 4, 210.
Click here to see how this site uses Cookies. View our privacy policy here.