1,2-Trans-Selective Synthesis of Glycosyl Boranophosphates and Their Utility as Building Blocks for the Synthesis of Phosphodiester-Linked Disaccharides
1,2-Trans-Selective Synthesis of Glycosyl Boranophosphates and Their Utility as Building Blocks for the Synthesis of Phosphodiester-Linked Disaccharides
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DOI：
10.1021/jo902725g
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发表时间：
2010-04-02
影响因子：
3.6
通讯作者：
Wada, Takeshi
中科院分区：
文献类型：
--
作者：
Sato, Kazuki;Oka, Natsuhisa;Wada, Takeshi
以碘化糖基化硼磷酸二甲酯为原料，制备了高1,2-反选择性硼磷酸糖基衍生物。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。合成的糖基硼磷酸三酯转化为相应的硼磷酸二酯，并与适当保护的单糖缩合，得到与硼磷酸异聚键连接的双糖。此外，双糖作为相应的磷酸二酯连接双糖的前体。整个硼磷酸二糖的合成过程及其转化为磷酸二酯二糖的过程产率都很好，且不损失其端粒位置的立体不纯性，表明该方法可用于合成非对纯磷酸糖基生物分子。
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.