Formation of 2-oxa- or 2-azabicyclo[3.3.0]octa-3,7-diene by a novel tandem intramolecular photo-cyclization of 2,4,6-tris(phenylthio)hepta-2,4,6-trienal derivatives

Abstract

The photo-reactions of 2,4,6-tris(phenylthio)hepta-2,4,6-trienal 1 and its 2,4-dinitrophenylhydrazone 5 gave the 2-oxa- or 2-azabicyclo[3.3.0]octa-3,7-dienes 2 and 9, respectively, via a photo-induced intramolecular tandem cyclization reaction.

References

1. J. A. Porco and S. L. Schreiber, Comprehensive Organic Synthesis, ed. B. M. Trost, I. Fleming and L. A. Paquette, Pergamon, New York, 1991, vol. 5, p. 151.
2. S. S. Bhagwat, P. R. Hamann, W. C. Still, S. Bunting and F. A. Fitzpatrick, J. Am. Chem. Soc., 1985, 107, 6372; S. S. Bhagwat, P. R. Hamann, W. C. Still, S. Bunting and F. A. Fitzpatrick, Nature, 1985, 315, 511; D. W. Norbeck and J. B. Kramer, J. Am. Chem. Soc., 1988, 110, 7217; Y. Kawahata, S. Takatsuto, N. Ikekawa, M. Murata and S. Omura, Chem. Pharm. Bull., 1986, 34, 3102.
3. M. Sakamoto, Y. Omote and H. Aoyama, J. Org. Chem., 1984, 49, 396; G. Pattenden and A. M. Birch, J. Chem. Soc., Chem. Commun., 1980, 1195; M. J. Begley, A. M. Birch and G. Pattenden, J. Chem. Soc., Chem. Commun., 1979, 235.
4. H. A. J. Carless, J. Beanland and S. Mwesigye-Kibonde, Tetrahedron Lett., 1987, 28, 5933; M. Riediker and J. Schwartz, J. Am. Chem. Soc., 1982, 104, 5842; K. Maruyama and Y. Kubo, J. Org. Chem., 1977, 42, 3215; P. H. Mazzocchi, L. Klingler, M. Edwards, P. Wilson and D. Shook, Tetrahedron Lett., 1983, 24, 143.
5. M. Yoshimatsu, K. Oguri, K. Ikeda and S. Gotoh, J. Org. Chem., 1998, 63, 4475.
6. Q. Tan and K. Nakanishi, J. Am. Chem. Soc., 1998, 120, 12 357 and references cited therein.
7. Selected data for 2: ν_max/cm^–1 1130 (ether); δ_H 0.91 (9H, s, Me × 3), 2.82 (1H, t, J 2, 6-H), 3.40 (1H, t, J 2, 5-H), 5.07 (1H, s, 8-H), 6.50 (1H, d, J 2, 3-H), 6.55–6.59 (2H, m, ArH), 7.01–7.07 (3H, m, ArH), 7.36–7.42 (5H, m, ArH), 7.46–7.51 (3H, m, ArH), 7.60–7.62 (2H, m, ArH); δ_C 28.60 (q × 3), 34.54 (s), 54.53 (d), 64.28 (d), 107.23 (s), 107.77 (s), 123.29 (d), 125.03 (d × 2), 126.16 (d), 128.89 (d × 2), 129.00 (d), 129.07 (d), 129.15 (d × 2), 129.57 (d × 2), 131.19 (s × 2), 132.13 (s), 132.46 (d × 2), 135.95 (d × 2), 150.10 (d), 150.65 (s); m/z 488 (M⁺)(Calc. for C₂₉H₂₈OS₃; C, 71.27; H, 5.77. Found: C, 71.12; H, 5.77%).
8. Crystal data for 2: C₂₉H₂₈OS₃M= 488.72, monoclinic, a= 9.007(2), b= 26.879(6), c= 10.945(2)Å, β= 99.34(2)°, V= 2614.7(9)ų, T= 298 K, space group P2₁/n, Z= 4, µ(Cu-Kα)= 2.728 mm^–1 , D_c= 1.214 Mg m^–3, 4284 reflections collected (Rigaku AFC5R diffractometer) of which 4096 were unique (R_int= 0.030) and 2720 were observed [I > 3.00σ(I)]. Solved by direct methods (MITHRIL90 and DIRDIF) and refined by full-matrix least-squares (teXsan) on F of all unique data to R= 0.056 (observed data), wR = 0.070 (all data). CCDC 182/1222. See http://www.rsc.org/suppdata/cc/1999/909/ for crystallograpic files in .cif format.
9. Selected data for 6: ν_max/cm^–1 3330 (NH), 1620, 1340 (NO₂); δ_H 1.28(9H, s, Me × 3), 4.47 (1H, s, 6-H), 6.29 (1H, s, 8-H), 6.47 (1H, s, 5-H), 6.57 (1H, s, 3-H), 6.74 (1H, d, J 10, ArH), 7.07–7.40 (15H, m, ArH), 8.13 (1H, dd, J 2 and 10 ArH), 9.02 (1H, br d, J 2, ArH), 10.06 (1H, s, NH); δ_C 30.39 (q × 3), 33.85 (s), 67.58 (d), 101.02 (s), 114.20 (d), 121.73 (s), 123.65 (d), 123.71 (d), 125.69 (d), 126.19 (d), 126.42 (d), 126.66 (d × 2), 128.23 (d), 128.45 (d × 2), 128.98 (d), 129.24 (d), 129.30 (d), 129.58 (s), 130.52 (d), 130.82 (s), 132.17 (d × 2), 132.74 (s), 133.92 (d), 133.98 (d), 134.08 (s), 138.33 (s), 138.68 (s), 140.31 (d), 147.70 (s), 152.78 (d); m/z 429 [M⁺–(Bu^t+(O₂N)₂C₆H₃NH)](Calc. for C₃₅H₃₂N₄O₄S₃: C, 62.85; H, 4.82; N, 8.38. Found: C, 62.71; H, 5.23; N, 7.96%).
10. M. Yoshimatsu, S. Gotoh, K. Ikeda and M. Komori, J. Org. Chem., 1998, 63, 6619.
11. A. G. Griesbeck, S. Buhr, M. Fiege, H. Schmickler and J. Lex, J. Org. Chem., 1998, 63, 3847.