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DOI: 10.1039/A903942B (Paper) Reference Section for: Chem. Commun., 1999, 1753-1754

A facile route to 3,7-cis-disubstituted cycloocta-1,5-diene-1,2,5,6- tetracarboxylates through photochemical [2 + 2]cycloaddition of 3-substituted cyclobutene-1,2-dicarboxylates and thermal isomerization†

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Hisayuki Watanabe, Yasuyuki Nakajima, Michiaki Adachi, Hiroyasu Hotta, Kazutaka Arai, Yoshiyasu Baba, Carole Noutary, Satsuki Ichikawa and Tetsuo Kusumoto

Abstract

Photochemical dimerization of 3-substituted cyclobutene-1,2-dicarboxylates followed by thermal isomerization gives regio- and stereo-selectively 3,7-cis-disubstituted cycloocta-1,5-diene-1,2,5,6-tetracarboxylates.

References

  1. T. Watanabe, K. Yasumoto, M. Murata, M. Tagawa, H. Narushima, T. Furusato, M. Kuwahara, M. Hanaue and T. Seki, Jpn. Kokai Tokkyo Koho, 1994, JP 06-184157, EP 582267, US 5346919; Search PubMed; Chem. Abstr., 1994, 121, 7432t Search PubMed.
  2. N. A. Petasis and M. A. Patane, Tetrahedron, 1992, 48, 5757 CrossRef CAS.
  3. Y. Baba, C. Noutary, S. Ichikawa, T. Kusumoto, H. Watanabe, M. Adachi, H. Hotta, Y. Nakajima, K. Arai and T. Hiyama, Synlett, 1997, 1393 CAS.
  4. Houben Weyl, 4/5a, 344–345, 352, 500–501; E. Vogel, O. Roos and K.-H. Disch, Justus Liebigs Ann. Chem., 1962, 653, 55 Search PubMed; D. Bellus, K. Bredow, H. Sauter and G. D. Weis, Helv. Chim. Acta, 1973, 56, 3004 CAS; K. I. Booker-Milburn, F. D. Jimenez and A. Sharpe, Synlett, 1995, 735 CAS.
  5. J. D. White, M. P. Dillon and R. J. Butlin, J. Am. Chem. Soc., 1992, 114, 9673 CrossRef CAS.
  6. Products 3d and 3e formed as inseparable mixtures of isomers due to asymmetric carbons of side chains.
  7. Crystal datafor C22H28O123i:M= 484.00, monoclinic, C2/c, a= 16.866(3), b= 10.100(2), c= 14.408(3)Å, β= 93.43(2)°, U= 2450.0(8)Å3 , T= 298 K, Z= 4, µ(Cu-Kα)= 1.009 mm –1 , 1980 reflections measured, 1873 unique (Rint= 0.065), R= 0.114, Rw= 0.117. Selected data for 3i:δH(CDCl3) 2.07 (s, 6H), 2.62 (dd, J1= 14.2, J2 6.3, 1H), 3.15 (t, J 14.0, 1H), 3.28–3.38 (m, 1H), 3.74 (s, 6H), 3.76 (s, 3H), 4.24 (dd, J1 11.2, J2 4.9, 1H), 4.31 (dd, J1 11.2, J2 6.1, 1H); m/z(FAB) 485 (M ++1), 453, 425, 411.
  8. The stereochemistry of 1a was confirmed to be 3,7-cis by X-ray crystallography, and further suggested the stereoselectivity of this route. Crystal data for C18H20O61a:M= 332.00, monoclinic, P21/a, a= 11.987(3), b= 13.131(3), c= 11.801(2)Å, β= 112.97(2)°, U= 1710.2(7)Å3 , T= 298 K, Z= 4, µ(Cu-Kα)= 0.7686 mm –1 , 2542 reflections measured, 1486 unique (Rint= 0.160), R= 0.098, Rw= 0.119. CCDC 182/1355. See http://www.rsc.org/suppdata/cc/1999/1753/ for crystallographic data in .cif format. Selected data for 1a:δH(CDCl3) 0.98 (t, J 7.2, 6H), 1.41–1.50 (m, 4H), 1.58–1.67 (m, 2H), 1.74–1.83 (m, 2H), 2.91–3.05 (m, 6H).
  9. M. Adachi, Y. Nakajima, H. Watanabe, H. Hotta, K. Arai, M. Tagawa, M. Futagawa, T. Furusato, H. Ohya, Y. Baba, C. Noutary, S. Ichikawa, T. Kusumoto and T. Hiyama, ‘The 21st IUPAC International Symposium on The Chemistry of Natural Products,’ Chinese Chem. Soc., Beijing, 1998, p. 169. Zopfiellin and its analogs 1a and 1c exhibit fungicidal activity at 100 ppm (in vitro) against Botorytis cinerea. Detailed results of the assay will be reported elsewhere.
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