Wilhelm, M. Mannova, M. Ausborn and P. Nuhn, Int. J. Pharm., 1994,
107, 99; A. Engel, K. Augsten, F. Wilhelm, S. K. Chatterjee and P.
Nuhn, Arch. Pharm., 1993, 326, 648; G. Förster, O. de la Cruz
Rodriguez, G. Bendas and P. Nuhn, Prog. Colloid Polym. Sci., 1995, 98,
201.
2 G. Wulff and G. Röhle, Angew Chem., Int. Ed. Engl., 1974, 13, 157; H.
Paulsen, ibid., 1982, 21, 155; R.R. Schmidt, ibid., 1986, 25, 212; J.
Thiem, Annu. Rep. Prog. Chem., Sect. B, 1985, 81, 311; K. Toshima and
K. Tatsuta, Chem. Rev., 1993, 93, 1503.
3 F. Wilhelm, S. K. Chatterjee, B. Rattay, P. Nuhn, R. Benecke and J.
Ortwein, Liebigs Ann., 1995, 1673.
4 M. Tanaka, M. Okita and I. Yamatsu, Carbohydr. Res., 1993, 241,
81.
glycoproteins in cell membranes, the immune system, receptors
of different bacterial cells9 and also the human P blood-group
system.10 They are therefore of great interest for cell-cell
recognition. We found that triacetyl-a-methylglycosides 4
react, in the presence of ferric chloride, with different
pentaacetyl monosaccharides to give heptaacetyl disaccharides
5 in high yield where the monosaccharide moiety is ster-
eoselectively a-orienteded to the glycosyl donor.
This work was supported by the Deutsche Forschungs-
gemeinschaft (Sonderforschungsbereich 197).
Notes and References
5 D. Kahne, D. Yang, J. J. Lim, R. Miller and E. Paguaga, J. Am. Chem.
Soc., 1988, 110, 8716.
† E-mail: nuhn@pharmazie.uni-halle.de
‡ General procedure: To a solution of pentaacetylmonosaccharide (2 g) in
CH2Cl2 below 5 °C was added slowly FeCl3 (1 equiv.), and the mixture was
stirred for 5 min. An equimolar amount of alcohol was then added to the
reaction mixture portionwise over 15 min. and stirred at room temperature.
Continuous TLC monitoring showed no significant formation of the
b-anomer. After completion of the reaction, indicated by the disappearance
of the alcohol by TLC ( there is always some transformation of the alcohol
to the acetate due to transesterification) the reaction mixture was poured into
sat. aq. sodium hydrogen carbonate and extracted with Et2O. Chromato-
graphy of the resultant mixture gave the expected glycoside. GCMS and
HPLC analysis showed it to be the a-anomer (Table 1), Pure anomer can be
obtained via preparative TLC. 13C and 1H NMR and mass spectroscopic and
other analytical data are identical to those reported previously (ref. 3).
6 S. Koto, N. Morishima, Y. Miyata and S. Zen, Bull. Chem. Soc. Jpn.,
1976, 49, 2639.
7 (a) S. Koto, N. Morishima. R. Kawahara, K. Ishikawa and S. Zen, Bull.
Chem. Soc. Jpn., 1982, 55, 1092; (b) P. Nuhn and G. Wagner, Z. Chem.,
1967, 7, 154; (c) N. Ikemoto, O. K. Kim, L.-C. Lo, V. Satyanarayana, M.
Chang and K. Nakanishi, Tetrahedron Lett., 1992, 33, 4295.
8 F. Dasgupta, P. P. Singh and H. C. Srivastava, Carbohydr. Res., 1980,
80, 346; V. Ferrieres, J.-N. Bertho and D. Plusquellee, Tetrahedron
Lett., 1995, 36, 2753.
9 H. Leffler and C. Svanborg-Eden, FEMS Microbiol. Lett., 1980, 8, 127;
G. Källenius, R. Möllby, S. B. Svenson, J. Winberg, A. Lundblad, S.
Svenssen and B. Cedergren, ibid., 1980, 7, 297.
10 M. Naiki and M. Kato, Vox Sang., 1979, 37, 30; R. R. Race and R.
Sanger, Blood Groups in Man, 6th edn., Blackwell, Oxford, 1975.
1 G. Bendas, F. Wilhelm, W. Richter and P. Nuhn, Eur. J. Pharm. Sci.,
1996, 4, 211; P. Nuhn, T. Pfaff, G. Bendas, F. Wilhelm and S. K.
Chatterjee, Arch. Pharm., 1994, 327, 429; A. Engel, G. Bendas, F.
Received in Cambridge, UK, 22nd April 1998; revised manuscript received,
15th June 1998; 8/04533J
1730
Chem. Commun., 1998