Department of Bimolecular System, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, Potsdam 14424, Germany.
Institute of Chemistry and Biochemistry, Freie Universität Berlin, Arnimallee 22, Berlin 14195, Germany.
Nat Commun. 2016 Sep 1;7:12482. doi: 10.1038/ncomms12482.
Automated glycan assembly (AGA) has advanced from a concept to a commercial technology that rapidly provides access to diverse oligosaccharide chains as long as 30-mers. To date, AGA was mainly employed to incorporate trans-glycosidic linkages, where C2 participating protecting groups ensure stereoselective couplings. Stereocontrol during the installation of cis-glycosidic linkages cannot rely on C2-participation and anomeric mixtures are typically formed. Here, we demonstrate that oligosaccharides containing multiple cis-glycosidic linkages can be prepared efficiently by AGA using monosaccharide building blocks equipped with remote participating protecting groups. The concept is illustrated by the automated syntheses of biologically relevant oligosaccharides bearing various cis-galactosidic and cis-glucosidic linkages. This work provides further proof that AGA facilitates the synthesis of complex oligosaccharides with multiple cis-linkages and other biologically important oligosaccharides.
自动化糖基化装配（AGA）已经从一个概念发展成为一种商业技术，可以快速提供长达 30 个残基的各种寡糖链。迄今为止，AGA 主要用于引入反式糖苷键，其中 C2 参与的保护基团确保立体选择性偶联。在顺式糖苷键的安装过程中，立体控制不能依赖于 C2 参与，通常会形成非对映异构体混合物。在这里，我们证明了使用带有远程参与保护基团的单糖砌块，通过 AGA 可以有效地制备含有多个顺式糖苷键的寡糖。通过自动合成具有各种顺式半乳糖基和顺式葡萄糖基键的具有生物相关性的寡糖来阐明该概念。这项工作进一步证明了 AGA 有助于合成具有多个顺式键和其他具有生物重要性的寡糖的复杂寡糖。
