Matsushita Kenya, Nakata Tomomi, Tamura Jun-ichi
Department of Chemistry and Biotechnology, Graduate School of Engineering, Tottori University, Koyamacho-Minami 4-101, Tottori 680-8552, Japan.
Department of Regional Environment, Faculty of Regional Sciences, Tottori University, Koyamacho-Minami 4-101, Tottori 680-8551, Japan.
Carbohydr Res. 2015 Apr 10;406:76-85. doi: 10.1016/j.carres.2015.01.007. Epub 2015 Jan 28.
Chondroitin sulfates (CSs) have characteristic bioactivities that depend on sulfation patterns. Chemically synthesized CS oligosaccharides are valuable tools for elucidating the relationship between structures and bioactivities. 2,2,2-Trichloroethyl (TCE) sulfated sugars are highly soluble in nonpolar solvents, which is useful for the synthesis of sulfated oligosaccharides. We herein synthesized CS-C [βGalNAc6S(1-4)βGlcA] (1) and CS-D [βGalNAc6S(1-4)βGlcA2S] (2) disaccharides that possessed sulfate groups by TCE sulfation at O-6 of GalNAc and an additional sulfate group at O-2 of GlcA, respectively. We revealed the superior functionalities of TCE sulfates during the synthesis of CS-C and -D, despite the unwanted side reactions in the acetamido-containing substrate.
硫酸软骨素（CSs）具有依赖于硫酸化模式的特征生物活性。化学合成的CS寡糖是阐明结构与生物活性之间关系的宝贵工具。2,2,2-三氯乙基（TCE）硫酸化糖在非极性溶剂中高度可溶，这对硫酸化寡糖的合成很有用。我们在此合成了CS-C [βGalNAc6S(1-4)βGlcA]（1）和CS-D [βGalNAc6S(1-4)βGlcA2S]（2）二糖，它们分别通过在GalNAc的O-6处进行TCE硫酸化以及在GlcA的O-2处额外引入一个硫酸基团而拥有硫酸基团。我们揭示了TCE硫酸盐在CS-C和-D合成过程中的优越功能，尽管在含乙酰胺基的底物中存在不必要的副反应。
