Department of Medical Genome Sciences, Graduate School of Frontier Sciences, The University of Tokyo, Bioscience Building 702, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8562, Japan.
J Org Chem. 2011 Apr 15;76(8):2648-59. doi: 10.1021/jo102584g. Epub 2011 Mar 24.
An efficient method for the synthesis of short oligo(α-D-glycosyl boranophosphate) derivatives by using an α-D-glycosyl phosphoramidite as a monomer unit was developed. The synthesis of oligomers was carried out by repeating a cycle consisting of the condensation of the monomer unit with a terminal hydroxy group of carbohydrates, boronation of the resultant phosphite intermediates, and terminal deprotection. The phosphoramidite monomer unit was synthesized from the corresponding glycosyl iodide and methyl N,N-diisopropylphosphonamidate in a highly α-selective manner. Di- and tri(α-D-glycosyl boranophosphate) derivatives obtained by the synthetic cycle were converted into the corresponding H-phosphonate diester derivatives, which were then used to synthesize di- and tri(α-D-glycosyl phosphate) derivatives including a fragment of Leishmania glycocalyx lipophosphoglycans.
开发了一种通过使用α-D-糖基磷酰胺作为单体单元高效合成短寡（α-D-糖苷基硼膦酸酯）衍生物的方法。通过重复一个循环进行低聚物的合成，该循环由单体单元与碳水化合物末端羟基的缩合、所得亚磷酸酯中间体的硼化以及末端脱保护组成。磷酰胺单体单元是通过相应的糖苷基碘化物和甲基 N，N-二异丙基磷酰胺以高度α-选择性的方式合成的。通过合成循环获得的二聚体和三聚体（α-D-糖苷基硼膦酸酯）衍生物被转化为相应的 H-膦酸二酯衍生物，然后将其用于合成包括利什曼原虫糖萼脂糖脂聚糖片段的二聚体和三聚体（α-D-糖苷基磷酸酯）衍生物。
