Sugar Silanes: Versatile Reagents for Stereocontrolled Glycosylation via Intramolecular Aglycone Delivery.
Sugar Silanes: Versatile Reagents for Stereocontrolled Glycosylation via Intramolecular Aglycone Delivery.
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DOI：
10.1039/c5sc00810g
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发表时间：
2015-06-01
期刊：
影响因子：
8.4
通讯作者：
Montgomery J
中科院分区：
文献类型：
--
作者：
Walk JT;Buchan ZA;Montgomery J
描述了一种新的醇类分子内糖基化方法。描述了一种新的醇类分子内糖基化方法。利用碳水化合物衍生的硅烷，醇的催化分解甲硅烷基化之后是分子内糖基化。硅烷位置和保护基团的适当组合允许高度选择性地接近β-甘露糖、α-葡糖或β-葡糖立体化学关系以及2-叠氮基-2-脱氧-β-葡糖-和2-脱氧-β-葡糖苷。从C-2或C-6位置的分子内糖苷配基递送分别提供1，2-顺式或1，2-反式糖苷。多功能受体底物，如羟基酮和二醇是耐受的，并以位点选择性方式糖基化。
A new method for the intramolecular glycosylation of alcohols is described. A new method for the intramolecular glycosylation of alcohols is described. Utilizing carbohydrate-derived silanes, the catalytic dehydrogenative silylation of alcohols is followed by intramolecular glycosylation. Appropriate combinations of silane position and protecting groups allow highly selective access to β-manno, α-gluco, or β-gluco stereochemical relationships as well as 2-azido-2-deoxy-β-gluco- and 2-deoxy-β-glucosides. Intramolecular aglycone delivery from the C-2 or C-6 position provides 1,2-cis or 1,2-trans glycosides, respectively. Multifunctional acceptor substrates such as hydroxyketones and diols are tolerated and are glycosylated in a site-selective manner.