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. 2010 Apr 2;75(7):2147-56. doi: 10.1021/jo902725g.
A highly 1,2-trans-selective synthesis of glycosyl boranophosphate derivatives by glycosylation of dimethyl boranophosphate with glycosyl iodides was developed. A study on the reaction mechanism indicated that the stereoselectivity of the reactions is controlled by neighboring group participation. The resultant glycosyl boranophosphate triesters were converted into the corresponding boranophosphate diesters and condensed with appropriately protected monosaccharides to give disaccharides linked with an anomeric boranophosphate linkage. Furthermore, the disaccharides worked as precursors of the corresponding phosphodiester-linked disaccharides. The whole synthesis of boranophosphate-linked disaccharides and their conversion to the phosphodiester-linked disaccharides were accomplished in good yields without loss of stereopurity at the anomeric position, indicating that the method is useful to synthesize diastereopure glycosyl phosphate-containing biomolecules.
通过二甲基硼膦与糖基碘化物的糖苷化反应，开发了一种高度 1,2-反式选择性合成糖基硼膦酸酯衍生物的方法。对反应机理的研究表明，反应的立体选择性受邻基参与的控制。所得的糖基硼膦酸三酯经转化为相应的硼膦酸二酯，并与适当保护的单糖缩合，得到以糖苷键连接的带有端基硼膦酸酯的二糖。此外，这些二糖可以作为相应的磷酸二酯键连接的二糖的前体。硼膦酸酯键连接的二糖的全合成及其转化为磷酸二酯键连接的二糖在没有立体纯度损失的情况下以良好的产率完成，表明该方法可用于合成非对映异构体纯的含糖苷磷酸酯的生物分子。
