具有预安装硫酸酯的肝素寡糖的差异合成。
Divergent heparin oligosaccharide synthesis with preinstalled sulfate esters.
机构信息
Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA.
出版信息
Chemistry. 2011 Aug 29;17(36):10106-12. doi: 10.1002/chem.201101108. Epub 2011 Jul 22.
Abstract
Traditional chemical synthesis of heparin oligosaccharides first involves assembly of the full length oligosaccharide backbone followed by sulfation. Herein, we report an alternative strategy in which the O-sulfate was introduced onto glycosyl building blocks as a trichloroethyl ester prior to assembly of the full length oligosaccharide. This allowed divergent preparation of both sulfated and non-sulfated building blocks from common advanced intermediates. The O-sulfate esters were found to be stable during glycosylation as well as typical synthetic manipulations encountered during heparin oligosaccharide synthesis. Furthermore, the presence of sulfate esters in both glycosyl donors and acceptors did not adversely affect the glycosylation yields, which enabled us to assemble multiple heparin oligosaccharides with preinstalled 6-O-sulfates.
摘要
肝素寡糖的传统化学合成首先涉及全长寡糖主链的组装，然后进行硫酸化。在此，我们报告了一种替代策略，其中在组装全长寡糖之前，将 O-硫酸盐作为三氯乙酯引入到糖基砌块上。这允许从常见的高级中间体中发散制备既带有硫酸酯基又不带硫酸酯基的砌块。在糖苷化以及肝素寡糖合成过程中遇到的典型合成操作过程中，O-硫酸盐酯均表现出稳定。此外，在糖基供体和受体中都存在硫酸酯基并不会对糖苷化产率产生不利影响，这使我们能够组装带有预安装的 6-O-硫酸盐的多种肝素寡糖。
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