SYNTHESIS OF 1,2-CIS-CONFIGURATED GLYCOSYLPHOSPHONATES
SYNTHESIS OF 1,2-CIS-CONFIGURATED GLYCOSYLPHOSPHONATES
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DOI：
10.1002/hlca.19860690105
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发表时间：
1986-01-01
影响因子：
1.8
通讯作者：
VASELLA, A
中科院分区：
文献类型：
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作者：
MEUWLY, R;VASELLA, A
描述了醛糖-1-磷酸酯的1，2-顺式构型的非等排膦酸酯类似物的合成。在三甲基甲硅烷基三氟甲磺酸酯存在下，用亚磷酸三烷基酯处理1-O-酰基-糖1、7、13和19，得到1，2-顺式构型的糖基膦酸酯2、4、8、10、14、16、20和22作为主要的端基异构体，1，2-反式构型的糖基膦酸酯3、5、9、11、15、17、21和23作为次要的端基异构体。将1，2-顺式构型的膦酸酯4、10、16和22脱保护，分别以高产率得到（β-D-吡喃葡萄糖基）膦酸酯6、（β-D-吡喃甘露糖基）膦酸酯12、（β-D-呋喃核糖基）膦酸酯18和（β-D-阿拉伯呋喃糖基）膦酸酯24。通过假定异头鏻盐中间体（如25和26）之间的平衡和通过形成五配位物质（如28）稳定顺式构型盐来解释1，2-顺式构型膦酸酯的优选形成。
A synthesis of 1,2‐cis‐configurated, non‐isosteric phosphonate analogues of aldose‐1‐phosphates is described. Treatment of 1‐O‐acyl‐glycoses1,7,13, and19with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2‐cis‐configurated glycosylphosphonates2,4,8,10,14,16,20, and22as the major anomers and the 1,2‐trans‐configurated glycosylphosphonates3,5,9,11,15,17,21, and23as the minor anomers. The 1,2‐cis‐configurated phosphonates4,10,16, and22were deprotected to give the (β‐D‐glucopyranosyl)phosphonate6, the (β‐D‐mannopyranosyl)phosphonate12, the (β‐D‐ribofuranosyl)phosphonate18, and the (β‐D‐arabinofuranosyl)phosphonate24, respectively, in high yields. The preferred formation of 1,2‐cis‐configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium‐salt intermediates (such as25and26) and a stabilization of thecis‐configurated salts through formation of a pentacoordinated species (such as28).