Potent, versatile, and stable: Thiazolyl thioglycosides as glycosyl donors
Potent, versatile, and stable: Thiazolyl thioglycosides as glycosyl donors
复制标题
DOI：
10.1002/anie.200454047
复制
发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Malysheva, NN
中科院分区：
文献类型：
--
作者：
Demchenko, AV;Pornsuriyasak, P;Malysheva, NN
3131 Angew。化学，2004,16,3131-3134 DOI: 10.1002/ange。200454047 2004 Wiley-VCH Verlag GmbH & Co. KGaA， Weinheim单位由o -糖苷键连接化学和/或酶合成复杂寡糖的重要性已经显现出来，因为这些化合物从天然来源的可用性很低。因此，许多糖基给体已被开发并用于低聚糖的合成。[2,3]尽管取得了巨大的进展，但目前还没有在溶液或聚合物载体上合成低聚糖的通用糖基化方法最近，我们对一类具有离去基SCR1= NR2的糖基供体（取代硫代氨基酰基衍生物）产生了兴趣。我们已经报道了s -苯并恶唑（SBox）糖苷的合成及其在立体选择性1,2 -顺式和1,2 -反式糖基化中的评价。[5,6]我们证明了SBox糖苷具有高立体选择性和非常高的产率。与相应的s -烷基/芳基苷相比，SBox苷在某些极端反应条件下（TfOH或NaH）的稳定性较低，这促使我们继续寻找该类的合适离去基。在这里，我们描述了新的糖基供体，噻唑基（Taz）硫甙的合成，它们在立体选择性糖基化中的应用，并评估了它们在聚合低聚糖合成中的实用性。
3131 Angew. Chem. 2004, 116, 3131–3134 DOI: 10.1002/ange. 200454047 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim units are joined by O-glycosidic bonds.[1] The importance of chemical and/or enzymatic synthesis of complex oligosaccharides has come to the fore because of the low availability of these compounds from natural sources. As a result, many glycosyl donors have been developed and employed in oligosaccharide synthesis.[2, 3] Despite enormous progress, no general glycosylation method for oligosaccharide synthesis in solution or on a polymer support has yet emerged.[4] Recently, we became interested in a class of glycosyl donors with the generic leaving group SCR1= NR2 (substituted thioimidoyl derivatives). We have already reported the synthesis of S-benzoxazolyl (SBox) glycosides and their evaluation in stereoselective 1, 2-cis and 1, 2-trans glycosylations.[5, 6] We demonstrated that the SBox glycosides provide high stereoselectivity and remarkably high yields. The lower stability of the SBox glycosides toward some extreme reaction conditions (triflic acid (TfOH) or NaH) in comparison to the corresponding S-alkyl/aryl glycosides prompted us to continue the search for suitable leaving groups of this class. Here, we describe the synthesis of novel glycosyl donors, the thiazolyl (Taz) thioglycosides, their application in stereoselective glycosylations, and an evaluation of their usefulness in convergent oligosaccharide synthesis.