Sommer Roman, Hauck Dirk, Varrot Annabelle, Imberty Anne, Künzler Markus, Titz Alexander
Chemical Biology of Carbohydrates, Helmholtz Institute for Pharmaceutical Research Saarland (HIPS), D-66123 Saarbrücken, Germany; Deutsches Zentrum für Infektionsforschung (DZIF), Standort Hannover-Braunschweig, Germany.
Centre de Recherche sur les Macromolécules Végétales (CERMAV-UPR5301), CNRS and Université Grenoble Alpes, BP53, F-38041 Grenoble cedex 9, France.
Beilstein J Org Chem. 2016 Dec 22;12:2828-2833. doi: 10.3762/bjoc.12.282. eCollection 2016.
Selenoglycosides are used as reactive glycosyl donors in the syntheses of oligosaccharides. In addition, such heavy atom analogs of natural glycosides are useful tools for structure determination of their lectin receptors using X-ray crystallography. Some lectins, e.g., members of the tectonin family, only bind to carbohydrate epitopes with O-alkylated ring hydroxy groups. In this context, we report the first synthesis of an -methylated selenoglycoside, specifically methyl 2--methyl-L-selenofucopyranoside, a ligand of the lectin tectonin-2 from the mushroom . The synthetic route required a strategic revision and further optimization due to the intrinsic lability of alkyl selenoglycosides, in particular for the labile fucose. Here, we describe a successful synthetic access to methyl 2--methyl-L-selenofucopyranoside in 9 linear steps and 26% overall yield starting from allyl L-fucopyranoside.
硒代糖苷在寡糖合成中用作活性糖基供体。此外，这类天然糖苷的重原子类似物是利用X射线晶体学确定其凝集素受体结构的有用工具。一些凝集素，例如tectonin家族的成员，仅与具有O-烷基化环羟基的碳水化合物表位结合。在此背景下，我们报道了首例α-甲基化硒代糖苷的合成，具体为2-α-甲基-L-硒代岩藻糖吡喃糖苷甲酯，它是来自蘑菇的凝集素tectonin-2的配体。由于烷基硒代糖苷固有的不稳定性，尤其是不稳定的岩藻糖，合成路线需要进行策略性修订和进一步优化。在此，我们描述了一条从L-岩藻糖吡喃糖苷烯丙酯出发，经9步线性反应、总收率26%成功合成2-α-甲基-L-硒代岩藻糖吡喃糖苷甲酯的方法。
