Auzanneau F I, Hanna H R, Bundle D R
Institute for Biological Sciences, National Research Council of Canada, Ottawa, Ontario.
Carbohydr Res. 1993 Feb 24;240:161-81. doi: 10.1016/0008-6215(93)84181-5.
Disaccharide analogs related to the 2-acetamido-2-deoxy-3-O-(alpha-L- rhamnopyranosyl)-beta-D-glucopyranose element of the Shigella flexneri Y polysaccharide antigen have been synthesized and used to map the binding site of murine monoclonal antibodies GC-4 and SYA/J6 by solid-phase inhibition assays. N-Acetyl, N-trifluoroacetyl and N-benzyloxycarbonyl derivatives of methyl-2-amino-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranoside 1, 3, and 4 were glycosylated by rhamnopyranosyl bromide and thioglycoside donors 5 and 6. These in turn provided access to a series of alpha-L-Rha p-(1-->3)-beta-D-GlcNp-(1-->O)-Me disaccharide glycosides with amino 13, N-acetyl 10, N-propionyl 14, N-pivaloyl 15, and N-trifluoroacetyl 11 functionalities. Congeners of the disaccharide 10 were synthesized with monodeoxy groups introduced at the C-4 and C-6 positions of the GlcNAc residues and at the C-4' position of the rhamnose unit. Chlorosulfation of the selectively protected disaccharide 24, followed by reduction of the 4-chloro-4-deoxy compound 25, was used to prepare the 4-deoxy congener 27, while the C-6 and C-4' deoxy derivatives 31 and 23 were assembled from their respective pre-functionalized monosaccharide building blocks 29 and 19.
已合成了与福氏志贺菌Y多糖抗原的2-乙酰氨基-2-脱氧-3-O-(α-L-鼠李吡喃糖基)-β-D-葡萄糖吡喃糖单元相关的二糖类似物，并通过固相抑制试验用于定位鼠单克隆抗体GC-4和SYA/J6的结合位点。甲基-2-氨基-4,6-O-亚苄基-2-脱氧-β-D-葡萄糖吡喃糖苷1、3和4的N-乙酰基、N-三氟乙酰基和N-苄氧羰基衍生物用溴代鼠李吡喃糖苷和硫代糖苷供体5和6进行糖基化。这些进而提供了一系列具有氨基13、N-乙酰基10、N-丙酰基14、N-新戊酰基15和N-三氟乙酰基11官能团的α-L-Rha p-(1→3)-β-D-GlcNp-(1→O)-Me二糖糖苷。合成了二糖10的同系物，在GlcNAc残基的C-4和C-6位置以及鼠李糖单元的C-4'位置引入了单脱氧基团。对选择性保护的二糖24进行氯磺化，然后还原4-氯-4-脱氧化合物25，用于制备4-脱氧同系物27，而C-6和C-4'脱氧衍生物31和23则由它们各自的预官能化单糖构建块29和19组装而成。
