Synthesis of the monosaccharide units of the O-specific polysaccharide of Shigella sonnei

被引:69
作者
Medgyes, A
Farkas, E
Liptak, A
Pozsgay, V
机构
[1] LAJOS KOSSUTH UNIV,INST BIOCHEM,H-4010 DEBRECEN,HUNGARY
[2] HUNGARIAN ACAD SCI,RES GRP CARBOHYDRATES,H-4010 DEBRECEN,HUNGARY
[3] NICHHD,DEV & MOL IMMUN LAB,NIH,BETHESDA,MD 20892
关键词
carbohydrate antigen; 2-acetamido-4-amino-2,4,6-trideoxy-D-galactose; 2-acetamido-2-deoxy-L-altruronic acid; glycoconjugate vaccine; lipopolysaccharide; O-specific polysaccharide; Shigella sonnei; TEMPO oxidation;
D O I
10.1016/S0040-4020(97)00145-2
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The monosaccharide components of the O-specific polysaccharide 1 of the lipopolysaccharide of the enteropathogenic bacterium Shigella sonnei were synthesized as their methyl glycosides 2 and 3 in their natural anomeric form. The key intermediate to the diamino-trideoxygalactose derivative 2 was ethyl 3-O-acetyl-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside (9) that was converted to its ditosylate 10. Regioselective deoxygenation at C-6 followed by nucleophilic displacement of the secondary tosyloxy group by azide afforded the 4-azido thioglycoside 13. Methyl trifluoromethanesulfonate-assisted methanolysis of 13 gave the O-glycoside 14. Replacement of the phthalimido by an acetamido group followed by catalytic reduction of the azido group led to the diamino-trideoxygalactose derivative 2, The precursor to the L-altruronic acid derivative 3 was methyl alpha-L-glucopyranoside (19) that was routinely converted to the benzylidene-protected 2,3-anhydro-allopyranoside 22. Regioselective opening of the epoxide ring by NaN3 afforded the 2 azido derivative 23 that was benzylated at HO-3. Hydrolytic removal of the benzylidene group followed by TEMPO oxidation of C-6 and subsequent esterification with MeI gave the key L-azido-altruronic acid intermediate 29 that was transformed to the acetamido-altruronic acid derivative 3. High resolution NMR data of the altruronic acid derivatives indicate that the conformation of their pyranose ring is crucially dependent on the substitution pattern: the 2-azido altruronic acid derivatives prefer the C-4(1) conformation whereas the 2-acetamido congeners exist preferentially in the C-1(4) conformation.
引用
收藏
页码:4159 / 4178
页数:20
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