Abstract
The first synthesis of the Neu5Gc analogue of SiaT n disaccharide, which can be detected in breast tumors by immunochemical methods, is reported. The regioselective sialylation of (3-trifluoroacetamidopropyl)-2-azido-2-deoxy-α-D-galactopyranoside with peracetate of the methyl ester ofN-acetoxyacetyl-neuraminic acid β-ethylthioglycoside in the presence ofN-iodosuccinimide and trifluoromethanesulfonic acid (or its trimethylsilyl ester) resulted in the derivatives of α- and β-sialyl(2→6)galactosaminide in 39 and 32% yields, respectively. The catalytic hydrogenolysis of the azido group and subsequentN- andO-acetylation of the α-anomer gave the peracetate of trifluoroacetamidopropyl glycoside. Removal of the protective groups led to glycoside Neu5Gcα2→6GalNAcα-O(CH2)3NH2. Using the Neu5Gc derivative with acetoxyacetyl groups at positions O9 and O4 as a donor increases the α-selectivity of sialylation to afford the α- and β-anomers in 69 and 8% yields, respectively.
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Abbreviations
- FAB-MS:
-
fast atom bombardment mass spectrometry
- Neu5Ac:
-
N-acetylneuraminic acid
- Neu5Gc:
-
N-glycolylneuraminic acid
- NIS:
-
N-iodosuccinimide
- SpOH:
-
HO(CH2)3NHCOCF3
- TfOH:
-
trifluoromethanesulfonic acid
- TMS-OTf:
-
trifluoromethanesulfonic acid trimethylsilyl ester
- TOF-MS:
-
252Cf plasma desorption time-of-flight mass spectrometry
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Simeoni, L.A., Byramova, N.E. & Bovin, N.V. Synthesis of disaccharide neu5Gcα(2–6)galNAcα as a spacer glycoside. Russ J Bioorg Chem 26, 183–191 (2000). https://doi.org/10.1007/BF02786344
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DOI: https://doi.org/10.1007/BF02786344