Esterase-catalysed regioselective 6-deacylation of hexopyranose per-acetates, acid-catalysed rearrangement to the 4-deprotected products and conversions of these into hexose 4- and 6-sulfates

Abstract

The esterase from Rhodosporidium toruloides has been used to catalyse the hydrolysis of a series of per-acetylated α-D-hexopyranoses and α-D-hexopyranosides. Per-acetylated glucose 4, mannose 6, N-acetylgalactosamine 8, galactose 10, methyl α-D-glucoside 12, methyl α-D-mannoside 14 and methyl α-D-galactoside 16 have been selectively cleaved at the C-6 position by the esterase to give the 6-OH derivatives 5, 7, 9, 11, 13, 15 and 17. Acid-catalysed rearrangement of acetates 5, 7, 13, 15, 11, 17 and 9 with 4→6 acetyl migration gives the corresponding 4-deprotected derivatives 22–28, respectively. Hydrolyses of β-D-glucose pentaacetate 20 and α-D-lactose octaacetate 21 have been attempted, but no hydrolyses have been observed. 1,2,3,6-Tetraacylated α-D-hexopyranoses 3 and 22, derivatives of N-acetylglucosamine and glucose respectively, and 2,3,6-triacetylated α-D-hexopyranosides 24 and 25, derivatives of glucose and mannose, respectively, have been hydrolysed by the esterase to the corresponding 4,6-dihydroxy acetates 29, 18, 30 and 31. Acylation of methyl α-D-glucopyranoside 32 catalysed by the esterase provides the C-6 monoacetate 33 and the C-3 monoacetate 34 in 4 and 5% yield, respectively. The sodium salts of N-acetylglucosamine, glucose, N-acetylgalactosamine, galactose and mannose 6-sulfates 38–42, respectively, are prepared in two steps from the 6-deacetylated hexopyranoses 2, 5, 9, 11 and 7, respectively. The sodium salts of N-acetylglucosamine, glucose and mannose 4-sulfates 43–45, respectively, are prepared in two steps from the 4-deacetylated precursors 3, 22 and 26 which are obtained via acid catalysed 4→6 acyl migration of compounds 2, 5 and 7.

References

1. (a) W. J. Hennen, H. M. Sweers, Y.-F. Wang and C.-H. Wong, J. Org. Chem., 1988, 53, 4939; (b) J.-F. Shaw and A. M. Klibanov, Biotechnol. Bioeng., 1987, 29, 648; (c) S. Tomic, D. Ljevakovic and J. Tomasic, Tetrahedron, 1993, 49, 10 977; (d) H. Waldmann, A. Heuser and A. Reidel, Synlett, 1994, 65; (e) H. M. Sweers and C.-H. Wong, J. Am. Chem. Soc., 1986, 108, 6421; (f) R. Löpez, C. Perez, A. Fernández-Mayoralas and S. Conde, J. Carbohydr. Chem., 1993, 12, 165; (g) S. Tomic, A. Trescec, D. Ljevakovic and J. Tomasic, Carbohydr. Res., 1991, 210, 191; (h) M. Kloosterman, E. W. J. Mosmuller, H. E. Schoemaker and E. M. Meller, Tetrahedron Lett., 1987, 28, 2989; (i) K. Kefurt, Z. Kefurtová, J. Jary, I. Horáková and M. Marek, Carbohydr. Res., 1992, 223, 137; (j) H. Waldmann, Liebigs Ann. Chem., 1988, 1175; (k) E. W. Holla, J. Carbohydr. Chem., 1990, 9, 113; (l) Y. Z. Frohwein and J. Leibowitz, Enzymologia, 1961, 23, 202, 208; (m) G.-T. Ong, K.-Y. Chang, S.-H. Wu and K.-T. Wang, Carbohydr. Res., 1994, 265, 311; (n) K.-Y. Chang, S.-H. Wu and K.-T. Wang, Carbohydr. Res., 1991, 222, 121; (o) G.-T. Ong, S.-H. Wu and K.-T. Wang, Bioorg. Med. Chem. Lett., 1992, 2, 161.
2. D. Chaplin, D. H. G. Crout, S. Bornemann, D. W. Hutchinson and R. Khan, J. Chem. Soc., Perkin Trans. 1, 1992, 235.
3. R. Khan, L. Gropen, P. A. Konowicz, M. Matulova and S. Paoletti, Tetrahedron Lett., 1993, 34, 7767.
4. J. M. Sugihara, Adv. Carbohydr. Chem., 1953, 8, 1; S. J. Angyal and G. J. H. Melrose, J. Chem. Soc., 1965, 6494; 6501; W. A. Bonner, J. Org. Chem., 1959, 24, 1388.
5. R. Albert, K. Dax, A. E. Stütz and H. Weidmann, J. Carbohydr. Chem., 1983, 2, 279.
6. (a) M. Therisod and A. M. Klibanov, J. Am. Chem. Soc., 1986, 108, 5638; (b) A. Ghogare and G. S. Khumar, J. Chem. Soc., Chem. Commun., 1989, 1522; (c) M. Degueil-Castaing, B. De Jeso, S. Drouillard and B. Maillard, Tetrahedron Lett., 1987, 28, 953; (d) Y.-F. Wang, J. J. Lalonde, M. Momongan, D. E. Bergbreiter and C.-H. Wong, J. Am. Chem. Soc., 1988, 110, 7200; (e) K. Faber, Biotransformations in Organic Chemistry, Springer-Verlag, Berlin-Heidelberg, 1992, p. 259; (f) F. Ledl and E. Schleicher, Angew. Chem., Int. Ed. Engl., 1990, 29, 565; (g) D. Bianchi, P. Cesti and E. Battistel, J. Org. Chem., 1988, 53, 5531; (h) B. Berger, C. G. Rabiller, K. Konigsberger, K. Faber and H. Griengl, Tetrahedron: Asymmetry, 1990, 1, 541; (i) F. Theil and H. Schick, Synthesis, 1991, 533; (j) E. W. Holla, Angew. Chem., Int. Ed. Engl., 1989, 28, 220; (k) F. Björkling, S. E. Godtfredson and O. Kirk, J. Chem. Soc., Chem. Commun., 1989, 934; (l) K. Adelhorst, F. Björkling, S. E. Godtfredson and O. Kirk, Synthesis, 1990, 112; (m) J. Fabre, D. Betbeder, F. Paul, P. Monsan and J. Perie, Tetrahedron, 1993, 49, 10 877; (n) M. Therisod and A. M. Klibanov, J. Am. Chem. Soc., 1987, 109, 3977; (o) F. Nicotra, S. Riva, F. Secundo and L. Zuchelli, Tetrahedron Lett., 1989, 30, 1703; (p) P. Ciuffreda, D. Colombo, F. Ronchetti and L. Toma, J. Org. Chem., 1990, 55, 4190; (q) D. Colombo, F. Ronchetti and L. Toma, Tetrahedron, 1991, 47, 103; (r) M. J. Chinn, G. Iacazio, D. G. Spackmann, N. J. Turner and S. M. Roberts, J. Chem. Soc., Perkin Trans. 1, 1992, 661; (s) L. Panza, Luisetti, E. Crociati and S. Riva, J. Carbohydr. Chem., 1993, 12, 125; (t) D. Colombo, F. Ronchetti, A. Scala, I. M. Taino and P. A. Taino, J. Carbohydr. Chem., 1994, 13, 611; (u) R. López, E. Montero, F. Sánchez, J. Cañada and A. Fernández-Mayoralas, J. Org. Chem., 1994, 59, 7027; (v) S. Riva, J. Chopineau, A. P. G. Kieboom and A. M. Klibanov, J. Am. Chem. Soc., 1988, 110, 584; (w) S. Cai, S. Hakomori and T. Toyokuni, J. Org. Chem., 1992, 57, 3431; (x) G. Carrea, S. Riva, F. Secundo and B. Danieli, J. Chem. Soc., Perkin Trans. 1, 1989, 1057; (y) H.-O. Park, D.-S. Lee and S.-C. Shim, Biotechnol. Lett., 1992, 14, 111; (z) I. Ikeda and A. M. Klibanov, Biotechnol. Bioeng., 1993, 42, 788.
7. D. T. Hurst and A. G. McInnes, Can. J. Chem., 1965, 43, 2004; R. W. Jeanloz and D. A. Jeanloz, J. Am. Chem. Soc., 1957, 79, 2579.
8. T. P. Skelton, L. V. Hooper, V. Srivastava, O. Hindsgaul and J. U. Baenziger, J. Biol. Chem., 1991, 266, 17 142 (and references cited therein).
9. J. U. Baenziger and E. D. Green, Biochim. Biophys. Acta, 1988, 947, 287; R. G. Spiro and V. D. Bhoyroo, J. Biol. Chem., 1988, 263, 14 351.
10. T. Krusius, J. Finne, R. K. Margolis and R. U. Margolis, J. Biol. Chem., 1986, 261, 8237; T. Krusius, V. N. Reinhold, R. K. Margolis and R. U. Margolis, Biochem. J., 1987, 245, 229; J. Finne, Ciba Found. Symp., 1989, 145(Carbohydr. Recognit. Cell. Funct.), 173.
11. A. Pinter and R. W. Compans, J. Virol., 1975, 16, 589.
12. C. C. Rider, Biochem. Soc. Trans., 1992, 20, 291.
13. M. V. Dennis, C. B. Watson and A. Heifetz, J. Cell Sci., 1984, 67, 121; L. Roux, S. Holojda, G. Sundblad, H. H. Freeze and A. Varki, J. Biol. Chem., 1988, 263, 8879; K. Sugahara, I. Yamashina, P. De Waard, H. Van Halbeek and J. F. G. Vliegenthart, J. Biol. Chem., 1988, 263, 10 168; G. Sundblad, S. Holojda, L. Roux, V. Varki and H. H. Freeze, J. Biol. Chem., 1988, 263, 8890.
14. J. K. Welply, J. L. Keene, J. J. Schmuke and S. C. Howard, Biochim. Biophys. Acta, 1994, 1197, 215; Y. Imai, L. A. Lasky and S. D. Rosen, Nature, 1993, 361, 555.
15. H. Nakahima, O. Yoshida, T. S. Tochikura, T. Yoshida, T. Mimura, Y. Kido, Y. Motoki, Y. Kaneko, T. Uryu and N. Yamamoto, Jpn. J. Cancer Res., 1987, 78, 1164; I. Yamamoto, K. Takayama, K. Honma, T. Gonda, K. Matsuzaki, K. Hatanaka, T. Uryu, O. Yoshida and H. Hakashima, Carbohydr. Polym., 1991, 14, 53; T. Uryu, N. Ikushima, K. Katsuraya, T. Shoji, N. Takahashi, T. Yoshida, K. Kanno, T. Murkami, H. Nakashima and N. Yamamoto, Biochem. Pharmacol., 1992, 43, 2385.
16. W. J. Chambers and T. N. Oeltmann, J. Immunol., 1986, 137, 1469.
17. D. R. Coombe, C. R. Parish, I. A. Ramshaw and J. M. Snowden, Int. J. Cancer, 1987, 39, 82.
18. J. R. Turvey, Adv. Carbohydr. Chem., 1965, 20, 183 (and references therein) R. L. Whistler, W. W. Spencer and J. N. BeMiller, Methods Carbohydr. Chem., 1963, 2, 298; P. J. Archbald, M. D. Fenn and A. B. Roy, Carbohydr. Res., 1981, 93, 177; V. M. Doctor and D. Esho, Carbohydr. Res., 1983, 121, 312.
19. E. G. V. Percival, J. Chem. Soc., 1945, 119.
20. R. B. Duff, J. Chem. Soc., 1949, 1597.
21. S. Coffey, G. W. Driver, D. A. W. Fairweather and F. Irving, Br. Pat., 642 206, 1950; M. L. Wolfrom and T. M. Shen Han, J. Am. Chem. Soc., 1959, 81, 1764.
22. A. G. Lloyd, Nature, 1959, 183, 109; S. Peat, J. R. Turvey, M. J. Clancy and T. P. Williams, J. Chem. Soc., 1960, 4761.
23. A. G. Lloyd, Biochem. J., 1962, 83, 455.
24. A. G. Lloyd, Biochem. J., 1960, 75, 478.
25. K. B. Guiseley and P. M. Ruoff, J. Org. Chem., 1961, 26, 1248.
26. T. Utamara, K. Kuromatsu, K. Sawa, K. Koizumi and T. Shingu, Chem. Pharm. Bull., 1986, 34, 2341.
27. M. Bouchra, P. Calinand and J. Gelas, Carbohydr. Res., 1995, 267, 227.
28. G. Jackson, H. F. Jones, S. Petursson and J. M. Webber, Carbohydr. Res., 1982, 102, 147.
29. E. G. Gros and E. M. Gruñeiro, Carbohydr. Res., 1970, 14, 409.
30. R. Albert, K. Dax, A. E. Stütz and H. Weidmann, J. Carbohydr. Chem., 1983, 2, 279.
31. J. R. Turvey and T. P. Williams, J. Chem. Soc., 1962, 2119.