Kaifu R, Osawa T
Carbohydr Res. 1979 Mar;69:79-88. doi: 10.1016/s0008-6215(00)85753-5.
In order to use, as hapten inhibitors against various galactose-binding lectins, the derivatives of O-beta-D-galactopyranosyl-(1 leads to 3)-O-(2-acetamido-2-deoxy-alpha-D-galactopyranosyl)-L-serine, which is the common core structure of sugar chains of most mucins, the synthesis of these compounds was investigated. Koenigs-Knorr condensation of the 4,6-O-benzylidene derivative of O-(2-acetamido-2-deoxy-alpha-D-galactopyranosyl)-N-tosyl-L-serine methyl ester with 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide gave O-(2,3,4,L-tetra-O-acetyl-beta-D-galactopyranosyl)-(1 leads to 3)-O-(2-acetamido-4,6-O-benzylidene-2-deoxy-alpha-D-galactopyranosyl)-N-tosyl-L-serine. Deacetylation, followed by acid hydrolysis of the benzylidene group, gave O-beta-D-galactopyranosyl-(1 leads to 3)-O-2-acetamido-2-deoxy-alpha-D-galactopyranosyl)-N-tosyl-L-serine. A beta anomer at the glycoside linkage of the 2-acetamido-2-deoxy-D-galactose residue was also synthesized by the same procedure. Agaricus bisporus (mushroom) hemagglutinin was found to recognize the O-alpha-glycosyl linkage between 2-acetamido-2-deoxy-D-galactose and L-serine, in addition to the O-beta-D-galactopyranosyl-(1 leads to 3)-(2-acetamido-2-deoxy-D-galactose sugar sequence, for which Arachis hypogaea (peanut) and Bauhinia purpurea hemagglutinins were found to be specific. Ricinus communis hemagglutinin is more specific for the O-beta-D-galactopyranosyl-(1 leads to 4)-2-acetamido-2-deoxy-D-glucose (commonly found in serum glycoproteins) than for the O-beta-D-galactopyranosyl-(1 linked to 3)-2-acetamido-2-deoxy-D-galactose sequence. With Wistaria floribunda hemagglutinin, not much difference in the inhibitory activities of these two sugar sequences was observed, and O-(2-acetamido-2-deoxy-alpha-D-galactopyranosyl)-N-tosyl-L-serine was the strongest inhibitor against this lectin.
为了将O-β-D-吡喃半乳糖基-(1→3)-O-(2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖基)-L-丝氨酸的衍生物用作针对各种半乳糖结合凝集素的半抗原抑制剂，对这些化合物的合成进行了研究，该衍生物是大多数粘蛋白糖链的共同核心结构。O-(2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖基)-N-对甲苯磺酰基-L-丝氨酸甲酯的4,6-O-亚苄基衍生物与2,3,4,6-四-O-乙酰基-α-D-吡喃半乳糖基溴进行柯尼希斯-克诺尔缩合反应，得到O-(2,3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基)-(1→3)-O-(2-乙酰氨基-4,6-O-亚苄基-2-脱氧-α-D-吡喃半乳糖基)-N-对甲苯磺酰基-L-丝氨酸。脱乙酰化，然后对亚苄基进行酸水解，得到O-β-D-吡喃半乳糖基-(1→3)-O-(2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖基)-N-对甲苯磺酰基-L-丝氨酸。2-乙酰氨基-2-脱氧-D-半乳糖残基糖苷键处的β异头物也通过相同的步骤合成。发现双孢蘑菇（蘑菇）血凝素除了识别O-β-D-吡喃半乳糖基-(1→3)-(2-乙酰氨基-2-脱氧-D-半乳糖糖序列外，还识别2-乙酰氨基-2-脱氧-D-半乳糖与L-丝氨酸之间的O-α-糖苷键，花生（花生）和紫荆血凝素对该序列具有特异性。蓖麻血凝素对O-β-D-吡喃半乳糖基-(1→4)-2-乙酰氨基-2-脱氧-D-葡萄糖（常见于血清糖蛋白中）的特异性高于对O-β-D-吡喃半乳糖基-(1连接到3)-2-乙酰氨基-2-脱氧-D-半乳糖序列的特异性。对于紫藤血凝素，观察到这两个糖序列的抑制活性没有太大差异，并且O-(2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖基)-N-对甲苯磺酰基-L-丝氨酸是针对该凝集素的最强抑制剂。
