SYNTHESIS OF LIGANDS RELATED TO THE VIBRIO-CHOLERAE O-SPECIFIC ANTIGEN .2. IMPROVED SYNTHESIS AND THE CRYSTAL-STRUCTURE OF METHYL 4,6-DIDEOXY-4-(3-DEOXY-L-GLYCERO-TETRONAMIDO)-ALPHA-D-MANNOPYRANOSIDE, THE METHYL ALPHA-GLYCOSIDE OF THE INTRACATENARY REPEATING UNIT OF THE O-POLYSACCHARIDE OF VIBRIO-CHOLERAE O/1

被引:20
作者
GOTOH, M
BARNES, CN
KOVAC, P
机构
[1] NIDDK, BETHESDA, MD 20892 USA
[2] UNIV MISSOURI, DEPT CHEM, COLUMBIA, MO 65211 USA
关键词
O-Polysaccharide; Perosamine; Vibrio cholerae O:1; α-d-Mannopyranoside, methyl 4,6-dideoxy-4-(3-deoxy-l-glycero-tetronamido-);
D O I
10.1016/0008-6215(94)84039-3
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The crude product of deamination of the commercially available L-homoserine was acetylated and the 2-O-acetyl-3-deoxy-L-glycero-tetronolactone (18) formed was used to N-acylate methyl perosaminide (methyl 4-amino-4,6-dideoxy-alpha-D-mannopyranoside, 12) and its 2,3-O-isopropylidene derivative. The major product isolated from the reaction was the crystalline methyl 4-(4-O-acetyl-3-deoxy-L-glycero-tetronamido)-4,6-dideoxy-alpha-D-manno-pyranoside (1, 70-75%) resulting from acetyl group migration in the initially formed 2'-O-acetyl derivative. O-Deacetylation of 1 gave the title amide 2. Compound 2, obtained crystalline for the first time, was fully characterized, and its crystal structure was determined. Deoxytetronamido derivatives diastereomeric with 1 and 2, respectively, were obtained by the acylation of 12 with 2-O-acetyl-3-deoxy-D-glycero-tetronolactone (prepared from D-homoserine), and subsequent deacetylation. Structures of several byproducts of the reaction of 12 with 18 have been deduced from their spectral characteristics. Since these byproducts were various O-acetyl derivatives of 2, the title compound could be obtained in similar to 90% yield by deacetylating (Zemplen) the crude mixture of N-acylation products, followed by chromatography.
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页码:203 / 218
页数:16
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