Pozsgay V, Brisson J R, Jennings H J
National Research Council of Canada, Division of Biological Sciences, Ottawa, Ontario.
Carbohydr Res. 1990 Sep 19;205:133-46. doi: 10.1016/0008-6215(90)80134-o.
Syntheses of the propyl glycosides (1-3) of beta-D-Galp-(1----4)-beta-D-GlcpNAc, beta-D-Glcp-(1----6)-[beta-D-Galp-(1----4)]-beta-D-GlcpNAc, and beta-D-Galp-(1----4)-beta-D-Glcp-(1----6)-[beta-D-Galp-(1----)]-beta-D- GlcpNAc, respectively, are reported. Reaction of allyl 2-acetamido-3-O-benzyl-2-deoxy-6-O-(4-methoxybenzyl)-beta-D-glucopyranos ide with 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide under Hg(CN)2 catalysis, followed by oxidative removal of the 4-methoxybenzyl group, gave allyl 2-acetamido-3-O-benzyl-2-deoxy-4-O-(2,3,4,6-tetra-O-acetyl-beta-D- galactopyranosyl)-beta-D-glucopyranoside (10) O-deacetylation of which, followed by hydrogenolysis/hydrogenation, gave 1. Reaction of 10 with beta-D-glucopyranose penta-acetate and beta-lactose octa-acetate, under catalysis by trimethylsilyl trifluoromethanesulfonate, and treatment of the products as for 10 gave 2 and 3, respectively. Attempted glycosylation of 10 with 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl bromide under catalysis by Hg(CN)2 or silver trifluoromethanesulfonate gave an orthoester. Complete assignments of the 1H- and 13C-n.m.r. spectra of 1-3 are reported together with their carbon spin-lattice relaxation times which indicate that 3 assumes a compact instead of an extended shape.
分别报道了β-D-Galp-(1→4)-β-D-GlcpNAc、β-D-Glcp-(1→6)-[β-D-Galp-(1→4)]-β-D-GlcpNAc和β-D-Galp-(1→4)-β-D-Glcp-(1→6)-[β-D-Galp-(1→)]-β-D-GlcpNAc的丙基糖苷（1-3）的合成。在Hg(CN)₂催化下，烯丙基2-乙酰氨基-3-O-苄基-2-脱氧-6-O-(4-甲氧基苄基)-β-D-吡喃葡萄糖苷与2,3,4,6-四-O-乙酰-α-D-吡喃半乳糖基溴反应，随后氧化除去4-甲氧基苄基，得到烯丙基2-乙酰氨基-3-O-苄基-2-脱氧-4-O-(2,3,4,6-四-O-乙酰-β-D-吡喃半乳糖基)-β-D-吡喃葡萄糖苷（10），对其进行O-脱乙酰化，然后进行氢解/氢化反应，得到1。10与β-D-吡喃葡萄糖五乙酸酯和β-乳糖八乙酸酯在三甲基甲硅烷基三氟甲磺酸酯催化下反应，并按处理10的产物的方式处理，分别得到2和3。尝试在Hg(CN)₂或三氟甲磺酸银催化下，使10与2,3,4,6-四-O-乙酰-β-D-吡喃葡萄糖基溴进行糖基化反应，得到一种原酸酯。报道了1-3的¹H-和¹³C-核磁共振光谱的完整归属以及它们的碳自旋晶格弛豫时间，结果表明3呈现紧凑而非伸展的形状。
