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Monatshefte für Chemie / Chemical Monthly

, Volume 122, Issue 12, pp 1075–1088 | Cite as

Strukturelle Abwandlungen an N-Acetylneuraminsäure, 25. Mitt.: Synthese von Methyl-2-α-glycosiden von 4-epi-, 7-epi-, 8-epi- und 7,8-bis-epi-N-Acetylneuraminsäure

  • B. P. Bandgar
  • E. Zbiral
Organische Chemie Und Biochemie

Structural transformations of N-acetylneuraminic acid, XXV: Synthesis of methyl-2-α-glycosides of 4-epi-, 7-epi-, 8-epi-, and 7,8-bis-epi-N-acetylneuraminic acid

Abstract

The α-methylketoside of N-acetylneuraminic acid methylester (4) is transformed via the deacetylated compound5 into the 9,8-O-isopropylidenderivative6 which could be oxidized regioselectively by RuO4 to the corresponding 4-oxo-sialic acid analogue7. Reduction with the boraneammonia complex produces a 1:1 mixture of6 and the desired α-methylketoside of 9,8-O-isopropyliden-4-epi-N-acetyl-neuraminic acid methylester (8). Removing of the isopropylidene group gives the α-methylketoside of 4-epi-N-acetylneuraminic acid methylester (9), which was further transformed to the ammonium salt of 4-epi-N-acetylneuraminic acid α-methylketoside (10). On the other hand compound5 was turned into the 4,8,9-tri-O-t-butyldimethylsilylderivative11 a from which the corresponding 7-oxo-compound12 by oxidation with RuO4 derives. The reduction of12 with BH3 - NH3 yielded a 1:1 mixture of the starting material11 a and the desired 7-epi-derivative13 a which gives either via the purified peracetylated α-methylketosid of 7-epi-N-acetylneuraminic acid methylester (14) or a direct saponification the sodium salt of 7-epi-N-acetylneuraminic acid-α-methylketoside (15).

Applying the Königs-Knorr procedure to the peracetylated 8-epi-N-acetylneuraminic acid methylester (16) gives rise to the formation of a 1:1 mixture of the corresponding α- and β-methylketosides17 and18 besides traces of the corresponding 2,3-dideoxy-2,3-dideohydro-sialic acid derivative19. After chromatographic separation of17 further saponification leads to the sodium salt of 8-epi-N-acetylneuraminic acid-α-methylketoside (20). In an analogous procedure the sodium salt of 7,8-di-epi-N-acetylneuraminic acid-α-methylketoside (25) was prepared starting from the peracetylated 7,8-di-epi-N-acetylneuraminic acid methylester (21), whereby a mixture of the α- and β-methylketosides22 and23 was formed in a ratio 95:5 besides traces of the peracetylated 2,3-dideoxy-2,3-didehydrosialic acid methylester (24).

Keywords

Sialic acid analogues Methyl-α-ketosides of sialic acid analogues 

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Copyright information

© Springer-Verlag 1991

Authors and Affiliations

  • B. P. Bandgar
    • 1
  • E. Zbiral
    • 1
  1. 1.Institut für Organische ChemieUniversität WienWienÖsterreich

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