Stereocontrolled synthesis and reactivity of sugar acetylenes

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

Minoru Isobe, Rena Nishizawa, Seijiro Hosokawa and Toshio Nishikawa


Abstract

C-Glycosidation is of great significance in the organic synthesis of optically active materials, since it allows the introduction of carbon chains to sugar chirons and the use of sugar nuclei as a chiral pool as well as a carbon source. Silylacetylenes are sufficiently reactive to form ‘sugar acetylenes’ for the selective introduction of various acetylenic groups in an alpha-axial manner at the anomeric position of D-hexopyranose rings. 1,4-Anti induction, on the other hand, gives a different stereochemical outcome in the case of C-glycosidation of pentopyranose glycals. The mechanism of these reactions includes oxonium cation intermediates in which stereoelectronic and/or steric factors drive the direction of the incoming silylacetylene. Bis-C-glycosidation allows the introduction of sugars at both ends of some bis(trimethylsilyl)acetylenes. A 2,3-dideoxyglucose derivative provides the corresponding C-1 α-acetylenic compounds, which would increase the scope of C-glycosidation with silylacetylenes. In sugar acetylenes, the alkynyl group at the anomeric position of a pyranose ring is epimerized via a hexacarbonyldicobalt complex by treatment with trifluoromethanesulfonic acid. The three steps—cobalt complexation, acidic transformation and decomplexation—afford overall epimerization and thus one can obtain either the α- or β-alkynyl C-glycoside as desired. Ring opening of a dihydropyran derivative using Nicholas-type cation intermediates is also part of this study. Several sets of decomplexation conditions for endo-type acetylene–cobalt complexes provide various olefins possessing potential utility for synthesis. These methodologies have been utilized for the synthesis of polyoxygenated natural products and derivatives.


References

  1. Total Synthesis of Natural Products: The ‘Chiron’ Approach, Stephen Hanessian, Pergamon, Oxford, 1983 Search PubMed.
  2. M. Isobe, M. Kitamura and T. Goto, Chem. Lett., 1982, 1907 CAS; M. Kitamura, M. Isobe, Y. Ichikawa and T. Goto, J. Org. Chem., 1984, 49, 3517 CrossRef CAS; M. Kitamura, M. Isobe, Y. Ichikawa and T. Goto, J. Am. Chem. Soc., 1984, 106, 3252 CrossRef CAS.
  3. M. Isobe, Yukigousei Kagaku Kyoukaishi, 1994, 52, 968 Search PubMed.
  4. (a) Y. Ichikawa, K. Tsuboi, Y. Jiang, A. Naganawa and M. Isobe, Tetrahedron Lett., 1995, 36, 7101 CrossRef CAS; (b) Y. Jiang and M. Isobe, Tetrahedron, 1996, 52, 2877 CrossRef CAS; (c) K. Tsuboi, Y. Ichikawa, Y. Jiang, A. Naganawa and M. Isobe, Tetrahedron, 1997, 53, 5123 CrossRef CAS.
  5. M. Isobe, C. Yenjai and S. Tanaka, Synlett, 1994, 916 CrossRef CAS; C. Yenjai and M. Isobe, Tetrahedron, 1998, 54, 2509 CrossRef CAS.
  6. M. Isobe, Y. Ichikawa and T. Goto, Tetrahedron Lett., 1986, 27, 963 CrossRef CAS; M. Isobe, Y. Ichikawa, D.-L. Bai, H. Masaki and T. Goto, Tetrahedron, 1987, 43, 4767 CrossRef CAS.
  7. S. Danishefsky and J. F. Kerwin, J. Org. Chem., 1982, 47, 3803 CrossRef CAS.
  8. Y. Ichikawa, M. Isobe, M. Konobe and T. Goto, Carbohydr. Res., 1987, 171, 193 CrossRef CAS.
  9. T. Tsukiyama and M. Isobe, Tetrahedron Lett., 1992, 33, 7911 CrossRef CAS.
  10. (a) Data are partly taken from the Masters Thesis of M. Konobe, Nagoya University ( 1988); (b) T. Nishikawa and M. Isobe, unpublished results.
  11. Very recently we have found that trimethylsilyl(propargyl)silane can only react with OTBDPS protection, thus avoiding coordination to SnCl4 due to its steric bulkiness. R. Saeeng and M. Isobe, unpublished results.
  12. Data are partly taken from the Master Thesis of T. Tsukiyama, Nagoya University, 1992.
  13. T. Tsukiyama, S. C. Peters and M. Isobe, Synlett, 1993, 413 CrossRef CAS.
  14. A. Herunsalee, M. Isobe, Y. Fukuda and T. Goto, Synlett, 1990, 701 CrossRef CAS.
  15. M. Isobe and Y. Jiang, Tetrahedron Lett., 1995, 36, 567 CrossRef CAS.
  16. Y. Jiang, Y. Ichikawa and M. Isobe, Tetrahedron, 1997, 53, 5103 CrossRef CAS; K. Tsuboi, Y. Ichikawa and M. Isobe, Synlett, 1997, 713 CAS.
  17. K. C. Nicolaou, C. K. Hwang and M. E. Duggan, J. Chem. Soc., Chem. Commun., 1986, 925 RSC.
  18. D. Zhai, W. Zhai and R. M. Williams, J. Am. Chem Soc., 1988, 110, 2501 CrossRef CAS.
  19. C. Leteux and A. Veyrieres, J. Chem. Soc., Perkin Trans. 1, 1994, 2647 RSC.
  20. E. Alvarez, R. Perez, M. Rico, R. M. Rodriguez, M. C. Suarez and J. D. Martin, Synlett, 1996, 1082 CrossRef CAS.
  21. M. Stake, A. Morohashi, H. Oguri, T. Oishi, M. Hirama, N. Harada and T. Yasumoto, J. Am. Chem. Soc., 1997, 119, 11 325 CrossRef.
  22. S. Hosokawa, B. Kirschbaum and M. Isobe, Tetrahedron Lett., 1998, 39, 1917 CrossRef CAS.
  23. S. Hosokawa and M. Isobe, Synlett, 1995, 1179 CrossRef CAS; S. Hosokawa and M. Isobe, Synlett, 1996, 351 CrossRef CAS; M. Isobe, S. Hosokawa and K. Kira, Chem. Lett., 1996, 473 CAS.
  24. M. Miljkovic, D. Yeaglley, P. Deslongchamps and Y. L. Dory, J. Org. Chem., 1997, 62, 7597 CrossRef CAS.
  25. K. M. Nicholas, Acc. Chem. Res., 1987, 20, 207 CrossRef CAS and references cited therein.
  26. S. Tanaka, T. Tsukiyama and M. Isobe, Tetrahedron Lett., 1993, 34, 5757 CrossRef CAS; S. Tanaka and M. Isobe, Tetrahedron, 1994, 50, 5633 CrossRef CAS.
  27. S. Tanaka and M. Isobe, Tetrahedron Lett., 1994, 35, 7801 CrossRef CAS; S. Tanaka, N. Tatsuta, O. Yamashita and M. Isobe, Tetrahedron, 1994, 50, 12 883 CrossRef CAS; S. Tanaka and M. Isobe, Synthesis, 1995, 859 CrossRef CAS.
  28. H. Greenfield, H. W. Sternberg, R. A. Friedel, J. Wotiz, R. Markby and I. Wender, J. Am. Chem. Soc., 1956, 78, 120 CrossRef.
  29. A. V. Muehldorf, A. Guzman-Perez and A. F. Kluge, Tetrahedron Lett., 1994, 35, 8755 CrossRef CAS; S. L. Schreiber, M. T. Klimas and T. Sammakia, J. Am. Chem. Soc., 1987, 109, 5749 CrossRef CAS.
  30. M. Saha, B. Baphy and K. M. Nicholas, Tetrahedron Lett., 1986, 27, 915 CrossRef CAS; P. J. Harrington, Transition Metals in Total Synthesis, Wiley, New York, 1990, pp. 241–301 Search PubMed; T. F. Jamison, S. Shambayati, W. E. Crowe and S. L. Schreiber, J. Am. Chem. Soc., 1994, 116, 5505 Search PubMed; C. Mukai, O. Kataoka and M. Hanaoka, J. Org. Chem., 1995, 60, 5910 CrossRef CAS.
  31. T. Nakamura, T. Matsui, K. Tanino and I. Kuwajima, J. Org. Chem., 1997, 62, 3032 CrossRef CAS.
  32. S. Hosokawa and M. Isobe, Tetrahedron Lett., 1998, 39, 2609 CrossRef CAS.
  33. S. Hosokawa and M. Isobe, unpublished results.
Click here to see how this site uses Cookies. View our privacy policy here.