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Synthesis of phosphites and phosphates of neuraminic acid and their glycosyl donor properties — convenient synthesis of GM3

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Abstract

The importance and requirements for catalytic activation of sialyl donors are discussed, leading to the acid sensitive phosphite and phosphate moiety, respectively, as leaving group and nitriles as solvent. Therefore, from readily availableN-acetylneuraminic acid, derivative1 with phosphochloridites2a-f and Huenigs' base sialyl phosphites3a-f were prepared and isolated in high yields. Oxidation of3a, c withtert-butyl-hydroperoxide afforded the corresponding phosphates4a, c. As expected, phosphites3 could be activated in acetonitrile by catalytic amounts of TMSOTf; thus, from3a-e as donors and lactose derivatives8A, B as acceptors the ganglioside building blocks9A and9B, respectively, were obtained in good yields. The best results were obtained with diethyl phosphite derivative3a as sialyl donor, which exceeded by far the reults obtained with the corresponding phosphate derivative4a. Trisaccharide9B was transformed into known9A and into the fullyO-acetylated GM3-trisaccharide10.

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References

  1. Schauer R (1982)Adv Carbohydr Chem Biochem 40: 131–234; (1982)Sialic Acids — Chemistry, Metabolism and Function. Vienna: Springer-Verlag.

    Google Scholar 

  2. Okamoto K, Goto T (1990)Tetrahedron 46: 5835–57.

    Google Scholar 

  3. Prabhanhan H, Ishida H, Kiso M, Hasegawa A (1991)Trends Glycosci Glycotech 3: 231–232.

    Google Scholar 

  4. De Ninno MP (1991)Synthesis 583–93.

  5. Eschenfelder V, Brossmer R (1980)Carbohydr Res 78: 190–94.

    Google Scholar 

  6. van der Vleugel DJM, Zwikker JW, Vliegenthart JFG (1982)Carbohydr Res 105: 19–31.

    Google Scholar 

  7. Kiso M, Nakamura A, Hasegawa A (1987)J. Carbohydr Chem 6: 411–22.

    Google Scholar 

  8. Paulsen H, von Deessen U (1988)Carbohydr Res 175: 283–93.

    Google Scholar 

  9. Shimizu C, Achiwa K (1989)Chem Pharm Bull 37: 2258–60, and references therein.

    Google Scholar 

  10. Sugimoto M, Ogawa T (1985)Glycoconjugate J 2: 5–9.

    Google Scholar 

  11. Numata N, Sugimoto M, Shibayama S, Ogawa T (1988)Carbohydr Res 174: 73–85.

    Google Scholar 

  12. Okamoto K, Kondo T, Goto T (1986)Tetrahedron Lett 27: 5229–32.

    Google Scholar 

  13. Okamoto K, Kondo T, Goto T (1986)Tetrahedron Lett 27: 5233–36.

    Google Scholar 

  14. Okamoto K, Kondo T, Goto T (1986)Chemistry Lett 1449–52.

  15. Okamoto K, Kondo T, Goto T (1987)Bull Soc Chem Jpn 60: 631–36.

    Google Scholar 

  16. Okamoto K, Kondo T, Goto T (1987)Bull Soc Chem Jpn 60: 637–43.

    Google Scholar 

  17. Okamoto K, Kondo T, Goto T (1987)Tetrahedron 43: 5909–18.

    Google Scholar 

  18. Okamoto K, Kondo T, Goto T (1987)Tetrahedron 43: 5919–28.

    Google Scholar 

  19. Okamoto K, Kondo T, Goto T (1988)Tetrahedron 44: 1291–98.

    Google Scholar 

  20. Kondo T, Abe H, Goto T (1988)Chemistry Lett 1657–60.

  21. Ito Y, Ogawa T (1987)Tetrahedron Lett 28: 6221–24.

    Google Scholar 

  22. Ito Y, Ogawa T (1988)Tetrahedron Lett 29: 3987–90.

    Google Scholar 

  23. Ito Y, Ogawa T (1990)Tetrahedron 46: 89–102.

    Google Scholar 

  24. Kanie O, Kiso M, Nakamura J, Hasegawa A (1987)J Carbohydr Chem 6: 117–28.

    Google Scholar 

  25. Kanie O, Kiso M, Hasegawa A (1988)J Carbohydr Chem 7: 501–6.

    Google Scholar 

  26. Murase T, Ishida H, Kiso M, Hasegawa A (1988)Carbohydr Res 184: C1-C4.

    Google Scholar 

  27. Hasegawa A, Nagahama T, Ohki H, Kotta K, Ishida H, Kiso M (1991)J Carbohydr Chem 10: 493–98.

    Google Scholar 

  28. Hasegawa A, Nagahama T, Ohki H, Ishida H, Kiso M (1992)Carbohydr Res 212: 277–81.

    Google Scholar 

  29. Hasegawa A, Adachik, Yoshida M, Kiso M (1992)Carbohydr Res 230: 257–72.

    Google Scholar 

  30. Hasegawa A, Adachik, Yoshida M, Kiso M (1992)Carbohydr Res 230: 273–78.

    Google Scholar 

  31. Prabhanjan H, Aoyama K, Kiso M, Hasegawa A (1992)Carbohydr Res 233: 87–99.

    Google Scholar 

  32. Marra A, Sinaÿ P (1989)Carbohydr Res 187: 35–42.

    Google Scholar 

  33. Marra A, Sinaÿ P (1990)Carbohydr Res 195: 303–8.

    Google Scholar 

  34. Toepfer A (1989) Investigations for PhD thesis.

  35. Biberg W, Lönn H (1991)Tetrahedron Lett 32: 7453–56.

    Google Scholar 

  36. Biberg W, Lönn H (1991)Tetrahedron Lett 32: 7457–60.

    Google Scholar 

  37. Lönn H, Stenvall K (1992)Tetrahedron Lett 33: 115–16.

    Google Scholar 

  38. Schmidt RR, Rücker E (1980)Tetrahedron Lett 21: 1421–24.

    Google Scholar 

  39. Schmidt RR, Michel J (1985)J Carbohydr Chem 4: 141–69.

    Google Scholar 

  40. Schmidt RR, Behrendt MN, Toepfer A (1990)Synlett 694–96, and references therein.

  41. Schmidt RR (1992) InCarbohydrates — Synthetic Methods and Applications in Medicinal Chemistry (Ogura H, Hasegawa A, Suami T, eds), pp. 66–88. Tokyo: Kodansha.

    Google Scholar 

  42. Martin TJ, Schmidt RR (1992)Tetrahedron Lett 33:6123–26.

    Google Scholar 

  43. Schmidt RR Abstracts XVIth Int Carbohydr Symp, Paris, France.

  44. Kondo H, Ichikawa Y, Wong C-H (1992)J Am Chem Soc 114:8748–50.

    Google Scholar 

  45. Ogawa T, Seta A (1982)Carbohydr Res 110:C1-C4.

    Google Scholar 

  46. Ichikawa Y, Sim MM, Wong CH (1992)J Org Chem 57:2943–46.

    Google Scholar 

  47. Schmidt RR (1988) Abstracts XIVth Int Carbohydr Symp, Stockholm, Sweden, PL8.

  48. Hashimoto S, Honda T, Ikegami S (1989)J Chem Soc Chem Commun 685–87.

  49. Hashimoto S, Yanagiya Y, Honda T, Harada H, Ikegami S (1992)Tetrahedron Lett 33:3523–26.

    Google Scholar 

  50. Kuhn R, Lutz P, MacDonald ML (1966)Chem Ber 99:611–17.

    Google Scholar 

  51. Paulsen H, Tietz H (1984)Carbohydr Res 125:47–64, and references therein.

    Google Scholar 

  52. Jung KH, Hoch M, Schmidt RR (1989)Liebigs Ann Chem 1099–106.

  53. Kitajima A, Sugimoto M, Nukada T, Ogawa T (1984)Carbohydr Res 127:C1-C4.

    Google Scholar 

  54. Ogawa T, Sugimoto M (1984)Carbohydr Res 128:C1-C4.

    Google Scholar 

  55. Ogawa T, Sugimoto M (1985)Carbohydr Res 135:C5-C9.

    Google Scholar 

  56. Paulsen H, von Deessen U (1986)Carbohydr Res 146:147–53.

    Google Scholar 

  57. Schmidt RR, Zimmermann P (1986)Tetrahedron Lett 27:481–84.

    Google Scholar 

  58. Schmidt RR, Zimmermann P (1986)Angew Chem 98:722–23.

    Google Scholar 

  59. Schmidt RR, Zimmermann P (1986)Angew Chem Int Ed Engl 25:725–26.

    Google Scholar 

  60. Zimmermann P, Bommer R, Bär T, Schmidt RR (1988)J Carbohydr Chem 7:435–52.

    Google Scholar 

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Authors and Affiliations

  1. Fakultät Chemie, Universität Konstanz, D-7750, Konstanz, Germany

    Thomas J. Martin, Roberto Brescello, Alexander Toepfer & Richard R. Schmidt

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  1. Thomas J. Martin
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  2. Roberto Brescello
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  3. Alexander Toepfer
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  4. Richard R. Schmidt
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Martin, T.J., Brescello, R., Toepfer, A. et al. Synthesis of phosphites and phosphates of neuraminic acid and their glycosyl donor properties — convenient synthesis of GM3 . Glycoconjugate J 10, 16–25 (1993). https://doi.org/10.1007/BF00731182

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  • DOI: https://doi.org/10.1007/BF00731182

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