Preparative Route to Per-O-acetylated N-Acetyl- and N-(tert-Butoxycarbonyl)neuraminyl-α-(2→3)-galactosyl Disaccharide Glycosyl Donors by Regioselective Acetolysis of Sialyl-α-(2→3′)-lactose

Andrei A. Sherman; Olga N. Yudina; Bozhena S. Komarova; Yury E. Tsvetkov; Stefano Iacobelli; Nikolay E. Nifantiev

doi:10.1055/s-2005-869957

PAPER

Preparative Route to Per-O-acetylated N-Acetyl- and N-(tert-Butoxycarbonyl)neuraminyl-α-(2→3)-galactosyl Disaccharide Glycosyl Donors by Regioselective Acetolysis of Sialyl-α-(2→3′)-lactose

Andrei A. Sherman^a, Olga N. Yudina^a, Bozhena S. Komarova^a, Yury E. Tsvetkov^a, Stefano Iacobelli^b, Nikolay E. Nifantiev*^a
^a N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect 47, 119991 Moscow, Russia
Fax: +7(095)1358784; e-Mail: nen@ioc.ac.ru;
^b Department of Oncology and Neurosciences, Sections of Medical Oncology and Pathology, University ‘G. D’Annunzio’, Chieti 66100, Italy

Abstract

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Abstract

Per-O-acetylated N-acetylneuraminyl-α-(2→3)-galactopyranose was prepared in three steps in good overall yield from sialyl-α-(2→3′)-lactose by regioselective cleavage of the galactosyl-β-(1→4)-glucose linkage by acetolysis and then readily converted into the corresponding disaccharide 1-trichloroacetimidate or ethyl thioglycoside, valuable synthetic blocks for the preparation of complex sialylated oligosaccharides. The N-acetyl group in the disaccharide thioglycoside was replaced by an N-Boc one via intermediate formation of a mixed N-Ac-N-Boc imide followed by chemoselective de-N-acetylation with hydrazine hydrate in DMF. An example of application of the disaccharide thioglycoside for the preparation of a spacer-armed hexasaccharide SLe^x is described.

Key words

carbohydrates - oligosaccharide - cleavage - acetals - glycosides - regioselectivity

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