ISSN:
0947-3440
Keywords:
Glycosides, pyruvated
;
Sponge, marine
;
Microciona prolifera
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Treatment of phenyl 2,3,6,2′,3′-penta-O-benzoyl-1-thio-β-D-lactoside (7) with BF3 in methyl pyruvate afforded the corresponding phenyl 4′,6′-O-[(R)-1-(methoxycarbonyl)ethylidene]-1-thio-β-D-lactoside (9) in 91% yield. The latter was converted via bromide 10 into the corresponding lactal 11 the azidonitration of which afforded an unseparable mixture of the „gluco“- and „manno“-configurated azido nitrates 12 (97%). As an alternative, benzyl O-(β-D-galactopyrnosyl)-(1→4)-2-azido-2-deoxy-α-D-glucopyranoside (15) was prepared in two steps and 91% yield from the corresponding fully acetylated 2-azido-2-deoxylactosyl bromide 13 and was further modified in four steps to give the benzoylated benzyl 4′,6′-O-benzylidene-2-deoxy-2-[(2,2,2-trichloroethoxycarbonyl)amino]-α-D-lactoside 18 in 78% overall yield. The benzylidene acetal of the latter was cleaved to give the diol 19 the pyruvation of which as for compound 9 afforded the corresponding pyruvated lactosamine derivative 20 (81%). Hydrogenolysis of 20 followed by treatment with trichloroacetonitrile gave the corresponding pyruvated disaccharide trichloroacetimidate 22 (77%). Coupling of the latter with Z-protected 5-amino-1-pentanol followed by deblocking of the intermediates furnished 5-aminopentyl 2-acetamido-4′,6′-O-[(R)-1-carboxyethylidene]-2-deoxy-β-D-lactoside (2). Similarly, condensation of 22 with 5-[(benzyloxycarbonyl)amino]-pentyl 2,4-di-O-benzyl-β-L-fucopyranoside (25) followed by deblocking of the intermediate trisaccharide afforded 5-aminopentyl O-{4,6-O-[(R)-1-carboxyethylidene]-β-D-galactopyranosyl}-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranoside-(1→3)-β-L-fucopyranoside (3). Saccharides 2 and 3, represent fragments of the Microciona prolifera aggregation factor.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.1995199506136
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