Automated solid-phase synthesis of protected oligosaccharides containing β-mannosidic linkages
Automated solid-phase synthesis of protected oligosaccharides containing β-mannosidic linkages
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DOI：
10.1002/chem.200701864
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Seeberger, Peter H.
中科院分区：
文献类型：
--
作者：
Codee, Jeroen D. C.;Kroeck, Lenz;Seeberger, Peter H.
为了使自动化寡糖合成影响糖生物学，大多数碳水化合物的合成途径必须变得高效和常规。必须建立安装“困难”糖苷键的方法，并将其纳入整体合成概念。本文描述的是第一个自动化固相合成的寡糖含有挑战性的β-甘露糖苷键。羧苄基甘露糖苷结构单元被证明是有效的β-甘露糖基化试剂，并产生优异的转化率和良好至中等的选择性。[（三异丙基甲硅烷基）氧基]-甲基醚（Tom）作为正交的、侵入性最小的且易于裂解的保护基团，用于延长甘露糖的C3位。使用反相HPLC，所需的寡糖产物易于与含有不需要的立体异构体的副产物分离。本文所述的方法扩大了目前可通过自动化获得的碳水化合物的范围，因为许多生物学目的寡糖含有β-甘露糖苷键。
For automated oligosaccharide synthesis to impact glycobiology, synthetic access to most carbohydrates has to become efficient and routine. Methods to install "difficult" glycosidic linkages have to be established and incorporated into the overall synthetic concept. Described here is the first automated solid-phase synthesis of oligosaccharides containing the challenging beta-mannosidic linkage. Carboxybenzyl mannoside building blocks proved effective beta-mannosylation agents and resulted in excellent conversion and good to moderate selectivities. [(Triisopropylsilyl)oxy]-methyl ether (Tom), served as an orthogonal, minimally intrusive, and readily cleavable protecting group for the elongation of the C3 position of mannose. The desired oligosaccharide products were readily separated from by-products containing unwanted stereoisomers using reverse-phase HPLC. The methods described here expand the scope of carbohydrates currently accessible by automation as many oligosaccharides of biological interest contain beta-mannosidic linkages.