Oligosaccharide synthesis with glycosyl phosphate and dithiophosphate triesters as glycosylating agents
Oligosaccharide synthesis with glycosyl phosphate and dithiophosphate triesters as glycosylating agents
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DOI：
10.1021/ja016227r
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发表时间：
2001-10-03
影响因子：
15
通讯作者：
Seeberger, PH
中科院分区：
文献类型：
--
作者：
Plante, OJ;Palmacci, ER;Seeberger, PH
描述了一种从糖经1，2-脱水糖有效一锅合成α-和β-糖基磷酸和二硫代磷酸三酯的方法。糖基磷酸盐在用三甲基甲硅烷基三氟甲磺酸酯（TMSOTf）活化时作为合成β-糖苷、β-半乳糖苷、α-岩藻糖苷、α-甘露糖苷、β-葡糖醛酸和β-葡糖胺键的通用糖基化剂起作用.除了作为O-糖基化的有效供体外，糖基磷酸酯在S-糖苷和C-糖苷的制备中也是有效的。此外，还讨论了糖基磷酸酯与硅烷基化受体的酸催化偶联反应。合成了糖基二磷酸盐，并将其用作糖基供体。这种替代方法提供了与含有糖基的受体的相容性以形成β-糖苷。为了最小化保护基团操作，报道了用糖基磷酸酯的正交和区域选择性糖基化策略。描述了一种正交糖基化方法，该方法涉及在硫代糖苷受体存在下活化糖基磷酸供体，这是一种受体介导的区域选择性糖基化策略。另外，公开了利用α-和β-糖基磷酸酯的反应性差异的独特糖基化策略。这里概述的程序提供了在溶液中组装复杂寡糖的基础，并通过自动化固相合成与糖基磷酸构建块，专门或与其他捐助者。
Described is an efficient one-pot synthesis of alpha- and beta -glycosyl phosphate and dithiophosphate triesters from glycals via 1,2-anhydrosugars. Glycosyl phosphates function as versatile glycosylating agents for the synthesis of beta -glucosidic, beta -galactosidic, alpha -fucosidic, alpha -mannosidic, beta -glucuronic acid, and beta -glucosamine linkages upon activation with trimethylsilyl trifluoromethanesulfonate (TMSOTf). In addition to serving as efficient donors for O-glycosylations, glycosyl phosphates are effective in the preparation of S-glycosides and C-glycosides. Furthermore, the acid-catalyzed coupling of glycosyl phosphates with silylated acceptors is also discussed. Glycosyl ditbiophosphates are synthesized and are also used as glycosyl donors. This alternate method offers compatibility with acceptors containing glycals to form beta -glycosides. To minimize protecting group manipulations, orthogonal and regioselective, glycosylation strategies with glycosyl phosphates are reported. An orthogonal glycosylation method involving the activation of a glycosyl phosphate donor in the presence of a thioglycoside acceptor is described, as is an acceptor-mediated regioselective glycosylation strategy. Additionally, a unique glycosylation strategy exploiting the difference in reactivity of alpha- and beta -glycosyl phosphates is disclosed. The procedures outlined here provide the basis for the assembly of complex oligosaccharides in solution and by automated solid-phase synthesis with glycosyl phosphate building blocks, exclusively or in concert with other donors.