Syntheses, structure analyses, and reactions of 1,3,5-trioxepanes and related compounds

Abstract

Acid-catalysed condensations of 1,5- or 1,6-dicarbonyl compounds with ethylene glycol give 1,3,5-trioxepane derivatives as a result of neighbouring participation by the adjacent carbonyl group during the acetalization process. With trimethylene glycol, the related 1,3,5-trioxocanes have also been obtained. Reaction of the 1,3,5-trioxepanes with (a) Grignard reagents gives dialkyl-substituted cyclic ethers, (b) titanium tetrachloride–allyltributyltin gives diallyl-substituted cyclic ethers and (c) triethylsilane in the presence of trimethylsilyl triflate provides the corresponding cyclic ethers.

References

1. T. Mukaiyama and M. Murakami, Synthesis, 1987, 1043.
2. G. Mehta, K. S. Rao and N. Krishnamurthy, Tetrahedron, 1989, 45, 2743.
3. The examples of neighbouring participation in dicarbonyl compounds: (a) G. A. Molander and P. R. Eastwood, J. Org. Chem., 1996, 61, 1910; (b) H.-J. Wu, S.-H. Tsai and W.-S. Chung, Chem. Commun., 1996, 375; (c) K. Bowden and F. P. Malik, J. Chem. Soc., Perkin Trans. 2, 1992, 5; (d) W. Y. Lee, C. H. Park, H.-J. Kim and S. Kim, J. Org. Chem., 1994, 59, 878; (e) K. J. McCullough, T. Sugimoto, S. Tanaka, S. Kusabayashi and M. Nojima, J. Chem. Soc., Perkin Trans. 1, 1994, 643.
4. P. Brownbridge and T. H. Chan, Tetrahedron Lett., 1979, 4437.
5. W.-L. Cheng, S.-M. Yeh and T. Y. Luh, J. Org. Chem., 1993, 58, 5576.
6. A. Hosomi and H. Sakurai, Tetrahedron Lett., 1978, 2589.
7. (a) Y. Yamamoto and N. Asao, Chem. Rev., 1993, 93, 2207; (b) C. Hull, S. V. Mortlock and E. J. Thomas, Tetrahedron Lett., 1987, 28, 5343.
8. T. Tsunoda, M. Suzuki and R. Noyori, Tetrahedron Lett., 1979, 4679.
9. S. Hatakeyama, H. Mori, K. Kitano, H. Yamada and M. Nishiyama, Tetrahedron Lett., 1994, 35, 4367.
10. G. A. Olah, M. Arvanaghi and L. Ohannesian, Synthesis, 1986, 772.
11. T. Sugimoto, M. Nojima and S. Kusabayashi, J. Org. Chem., 1990, 55, 4221.
12. T. Fujisaka, M. Nojima and S. Kusabayashi, J. Org. Chem., 1985, 50, 275.
13. M. Miura, A. Ikegami, M. Nojima, S. Kusabayashi, K. J. McCullough and S. Nagase, J. Am. Chem. Soc., 1983, 105, 2414.
14. SHELXS-86 G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
15. SHELXTL/PC (Ver. 5.03), G. M. Sheldrick, Siemens Analytical X-ray Instruments Inc., Madison, WI, USA.