MERCURY IODIDE AS A CATALYST IN OLIGOSACCHARIDE SYNTHESIS
MERCURY IODIDE AS A CATALYST IN OLIGOSACCHARIDE SYNTHESIS
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DOI：
10.3891/acta.chem.scand.37b-0775
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发表时间：
1983-01-01
期刊：
影响因子：
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通讯作者：
MELDAL, M
中科院分区：
文献类型：
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作者：
BOCK, K;MELDAL, M
二糖4-O-α- D-吡喃甘露糖基-α- L-吡喃鼠李糖和三糖2-O-α- D-吡喃半乳糖基-4-O-β- D-甘露吡喃酰基-α- L-吡喃鼠李糖决定簇是沙门氏菌血清群A、B和D的重复单元的类似物，在糖基化反应中使用碘化汞作为催化剂合成。二糖和三糖的还原端被连接臂取代，用于共价连接至蛋白质载体。8-乙氧羰基辛-1-基2，3-二-O-苯甲酰基-α- L-吡喃鼠李糖苷与乙酰溴甘露糖在碘化汞存在下脱保护后得到二糖，产率为49%。通过嵌段合成制备三糖，其中6-O-乙酰基-4-O-烯丙基-2-O-（6-O-乙酰基-2-O-烯丙基-3，4-二-O-苯甲酰基-α- D-吡喃半乳糖基）-3-O-苄基-α- D-吡喃甘露糖基溴（21）和8-甲氧基羰基辛-1-基2，3-O-亚环己基-α- L-吡喃鼠李糖苷在碘化汞存在下进行缩合反应。这些条件以26%的产率得到三糖。二糖21通过HgI 2催化的保护的吡喃半乳糖基溴和4-O-烯丙基-1，6-脱水-3-O-苄基-β-吡喃半乳糖基溴的缩合来制备。D-吡喃甘露糖，然后进行乙酰解并与TiBr 4反应。
The disaccharide 4-O-.alpha.-D-mannopyranosyl-.alpha.-L-rhamnopyranose and the trisaccharide 2-O-.alpha.-D-galactopyranosyl-4-O-.beta.-D-mannopyransoyl-.alpha.-L-rhamnopyranose determinants, which are analogs of the repeating unit of Salmonella serogroup A, B and D, were synthesized using HgI2 as a catalyst in the glycosylation reaction. The reducing end of the di- and the trisaccharide was substituted with a linking arm for covalent attachment to a protein carrier. Reaction of 8-ethoxycarbonyloct-1-yl 2,3-di-O-benzoyl-.alpha.-L-rhamnopyranoside with acetobromomannose in the presence of HgI2 gave, after deprotection, the disaccharide in 49% yield. The trisaccharide was prepared by a block synthesis in which 6-O-acetyl-4-O-allyl-2-O-(6-O-acetyl-2-O-allyl-3,4-di-O-benzoyl-.alpha.-D-galactopyranosyl)-3-O-benzyl-.alpha.-D-mannopyranosyl bromide (21) and 8-methoxycarbonyloct-1-yl 2,3-O-cyclohexylidene-.alpha.-L-rhamnopyranoside were condensed in the presence of HgI2. These conditions gave the trisaccharide in 26% yield. The disaccharide 21 was prepared by HgI2 catalyzed condensation of the protected galactopyranosyl bromide and 4-O-allyl-1,6-anhydro-3-O-benzyl-.beta.-D-mannopyranose followed by acetolysis and reaction with TiBr4.