Polymer-supported solution synthesis of oligosaccharides: Probing glycosylations of MPEG-DOX-OH with 2-acetamidoglycopyranosyl derivatives

Synlett

Volumn 1996, Issue 2, 1996, Pages 159-162

  Hodosi, György ^a   Krepinsky, Jiri J ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1842435181     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5349     Document Type: Article

References (33)

1. Douglas, S. P.; Whitfield, D. M.; Krepinsky, J. J. J. Amer. Chem. Soc. 1991, 113, 5095.
2. a) Kandil, A. A.; Chan, N.; Chong, P.; Klein, M. Synlett 1992, 555;
3. b) Verduyn, R.; van der Klein, P. A. M.; Douwes, M.; van der Marel, G. A.; van Boom, J. H. Rec. Trav. Chim. Pays-Bas 1993, 112, 464;
4. c) Dreef-Tromp, C. M.; Willems, H. A. M.; Basten, J. E. M.; Westerduin, P.; van Boeckel, C. A. A. Abstracts, XVIIth Int. Carbohydr. Symposium 1994, 511.
5. Douglas, S.P.; Whitfield, D.M.; Krepinsky, J.J. J. Amer. Chem. Soc. 1995, 118, 2116.
6. Toshima, K.; Tatsuta, K. Chem. Revs. 1993, 93, 1503.
7. (a) Kiso, M.; Anderson, L. Carbohydr. Res. 1979, 71, C12;
8. (b) Matta, K.L.; Bahl, O.P. Carbohydr. Res. 1972, 21, 460.
9. Nakabayashi, J.; Warren, C.D.; Jeanloz, W.R. Carbohydr. Res. 1986, 150, C7.
10. Unpublished observations.
11. Ha,Hb (benzylic) 12.08.
12. 3).
13. 3).
14. 6a,6b 12.27.
15. This scission is presently under investigation. Mass spectrometric data indicate that in one case two glycol units were cleaved from the polyethylene glycol (Douglas, S.P., Pang, H.Y.S., unpublished). See also, Krepinsky, J.J. in Modern Methods of Carbohydrate Synthesis (Khan, S.A.; O'Neill, R.A., Eds.), Harwood Academic Publishers, pp. 194-224, 1995.
16. This scission is presently under investigation. Mass spectrometric data indicate that in one case two glycol units were cleaved from the polyethylene glycol (Douglas, S.P., Pang, H.Y.S., unpublished). See also, Krepinsky, J.J. in Modern Methods of Carbohydrate Synthesis (Khan, S.A.; O'Neill, R.A., Eds.), Harwood Academic Publishers, pp. 194-224, 1995.
17. Harris, J.M. J. Macromol. Sci.-Rev. Macromol. Chem. Phys., 1985, C25, 326.
18. (a) Lemieux, R.U. Chem. Can. 1964, 16, 14;
19. (b) Whitfield, D.M.; Douglas, S.P.; Tang, T.H.; Csizmadia, I.G.; Pang, H.Y.S.; Moolten, F.L.; Krepinsky, J.J. Can. J. Chem. 1994, 72, 2225;
20. (c) Leung, O.T.; Douglas, S.P.; Whitfield, D.M.; Pang, H.Y.S; Krepinsky, J.J. New. J. Chem. 1994, 18, 349, and the references therein.
21. 3O-PEG).
22. 3O-PEG).
23. 6a,6b 12.63.
24. Lemieux, R.U.; Driguez, H. J. Amer. Chem. Soc. 1975, 97, 4063.
25. Banoub, J.; Boulianger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
26. Conditions: PEG-DOX-OH. (1 equiv.), 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl chloride (14; 2 equiv.), silver triflate (1.5 equiv.) were refluxed in dichloromethane (50 °C, bath temp.) under stirring for 6 hours. The polymer-containing substances were precipitated with tert-butyl methyl ether, and the precipitate recrystallized from dry ethylalcohol.
27. a) Kuhn, R.; Kirschenlohr, W. Chem. Ber. 1953, 86, 1331;
28. b) Lee, Y.C.; Lee, R.T. Carbohydr. Res. 1974, 37, 193.
29. The procedure in the Ref. 6 was followed with the exception of using triethylsilyl triflate instead of trimethylsilyl triflate.
30. Stöckl, W.P.; Weidman, H. J. Carbohydr. Chem. 1989, 8, 169.
31. 3CONH+).
32. 1H NMR spectrum of 15 is at too low field for an ester.
33. N2 displacement of an anomeric α-leaving group, such as chloride, provides the required anomeric specificity; should an electron-deficient anomeric carbon be formed, a transition state analogous to one just described is expected to operate. (Equation Presented)