功能性稀有单糖2,3-二氨基-D-甘露糖醛酸的合成研究

Study on the synthesis of functional rare sugar 2,3-diamino-D-mannuronic acids

关键词:  2,3-二氨基-D-甘露糖醛酸  化学合成  1,2-顺式-糖苷键  亲核取代

Key words:  2,3-diamino-D-mannuronic acid  chemical synthesis  1,2-cis-glycosidic bond  nucleophilic substitution

摘要:

目的 合成两种功能性2,3-二-氨基-D-甘露糖醛酸糖苷,为研究其构效关系及生物医学应用提供物质基础。方法 以烯丙基D-阿洛糖苷为原料,经C3位SN2叠氮基亲核取代、C6位羟基氧化得到关键中间体3-叠氮基-D-葡萄糖醛酸,后经端基位连接臂组装、C3位叠氮基亲核取代、叠氮基还原以及氨基的选择性乙眯基和乙酰基修饰等反应制得两种目标产物。结果 所有中间体和目标产物结构均经1H NMR、13C NMR和HRMS确证,产物纯度经HPLC检测>99.0%。结论 两种功能性稀有糖苷的合成路线操作简便,目标产物纯度高,为后续其免疫活性研究提供物质基础。

Abstract:

To synthesize two functional 2,3-diamino-D-mannuronic acid glycosides for investigating their structure-activity relationships and potential biomedical applications. METHODS Starting with allyl D-allose as the starting material, the key intermediate 3-azido-D-glucuronic acid was synthesized by performing a nucleophilic substitution of the SN2 azide group at the C3 position and oxidizing the hydroxyl group at the C6 position. Subsequently, two target products were obtained by reactions involving linker assembly, nucleophilic substitution of the azide group at the C3 position, reduction of the azide group, and selective modification of the amino group through acetamidino and acetyl groups. RESULTS The structures of all intermediates and target products were confirmed using 1H NMR, 13C NMR, and HRMS, with the products purity exceeding 99.0% as determined by HPLC. CONCLUSION The synthetic route for these two functional rare glycosides is straightforward and the resulting products exhibit high purity, laying a solid foundation for future investigations into their immunological activities.