Tumor-associated antigen synthesis. Synthesis of the Gal-α-(1→3)-Gal-β-(1→4)-GlcNAc epitope : a specific determinant for metastatic progression ?
Tumor-associated antigen synthesis. Synthesis of the Gal-α-(1→3)-Gal-β-(1→4)-GlcNAc epitope : a specific determinant for metastatic progression ?
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DOI：
10.1002/jlac.1991199101113
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发表时间：
1991-07
影响因子：
2.8
通讯作者：
R. Schaubach;J. Hemberger;W. Kinzy
中科院分区：
文献类型：
--
作者：
R. Schaubach;J. Hemberger;W. Kinzy
可以开发与烷基间隔分子偶联的 Gal-α-(13)-Gal-β-(14)-GlcNAc 表位的通用合成方法。通过氧化二丁基锡和烯丙基溴在 D-乳醛上的作用，高产率地制备了重要的结构单元 3'-烯丙基-D-乳醛 6，并通过几个步骤转化为带有游离 3'-OH 基团的乳糖胺衍生物 13。与苄基化 D-半乳糖 18 的 β-三氯乙酰亚胺酯进行立体选择性糖苷化可产生高产率的三糖。通过去甲硅烷基化和三氯乙酰亚胺酯形成，然后用 9-羟基壬酸乙酯进行糖苷化，激活受保护的 Gal-α-(13)-Gal-β-(14)-GlcNAc 衍生物 21，在简单的两步脱保护后，以优异的产率提供了间隔基结合的三糖半抗原 24。三糖半抗原24在与免疫原性载体偶联后可以很容易地用作免疫原。
A versatile synthesis of the Gal-α-(13)-Gal-β-(14)-GlcNAc epitope coupled to an alkyl spacer molecule could be developed. The important building block 3′-allyl-D-lactal 6 was prepared in high yield by the action of dibutyltin oxide and allyl bromide on D-lactal and converted in several steps into the lactosamine derivative 13 with free 3′-OH group. Stereoselective glycosidation with the β-trichloroacetimidate of benzylated D-galactose 18 led to the trisaccharide in high yield. Activation of the protected Gal-α-(13)-Gal-β-(14)-GlcNAc derivative 21 by desilylation and trichloroacetimidate formation followed by glycosidation with ethyl 9-hydroxynonanoate furnished the spacer-bound trisaccharide hapten 24 in excellent yield after simple two-step deprotection. The trisaccharide hapten 24 can easily be used as immunogen after coupling to an immunogenic carrier.