Enhanced stereoselectivity of alpha-mannosylation under thermodynamic control using trichloroacetimidates.
Carbohydr Res
; 345(8): 999-1007, 2010 May 27.
Article
em En
| MEDLINE
| ID: mdl-20381793
ABSTRACT
O-Specific polysaccharides of Vibrio cholerae O1, serotypes Inaba and Ogawa, consist of alpha-(1-->2)-linked N-(3-deoxy-L-glycero-tetronyl)perosamine (4-amino-4,6-dideoxy-D-mannose). The blockwise synthesis of larger fragments of such O-PSs involves oligosaccharide glycosyl donors that contain a nonparticipating 2-O-glycosyl group at the position vicinal to the anomeric center where the new glycosidic linkage is formed. Such glycosyl donors may bear at C-4 either a latent acylamino (e.g., azido) or the 3-deoxy-L-glycero-tetronamido group. While monosaccharide glycosyl donors, even those bearing a nonparticipating group at O-2 (e.g., methyl), and the 4-N-(3-deoxy-L-glycero-tetronyl) side chain form alpha-linked oligosaccharides with excellent stereoselectivity, alpha-mannosylation with analogous oligosaccharide donors in this series is adversely affected by the presence of the side chain. Consequently, the unwanted beta-product is formed in a considerable amount. Conducting the reaction at elevated temperature under thermodynamic control substantially enhances formation of the alpha-linked oligosaccharide. This effect is much more pronounced when glycosyl trichloroacetimidates, rather than thioglycosides or glycosyl chlorides, are used as glycosyl donors.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Antígenos O
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Vibrio cholerae O1
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Cloroacetatos
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Manose
Idioma:
En
Ano de publicação:
2010
Tipo de documento:
Article