1-N-GLYCYL BETA-OLIGOSACCHARIDE DERIVATIVES AS STABLE INTERMEDIATES FOR THE FORMATION OF GLYCOCONJUGATE PROBES
1-N-GLYCYL BETA-OLIGOSACCHARIDE DERIVATIVES AS STABLE INTERMEDIATES FOR THE FORMATION OF GLYCOCONJUGATE PROBES
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DOI：
10.1021/bi00159a012
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发表时间：
1992-11-10
期刊：
影响因子：
2.9
通讯作者：
DWEK, RA
中科院分区：
文献类型：
--
作者：
MANGER, ID;RADEMACHER, TW;DWEK, RA
在碳酸氢铵中孵育还原糖是一种简单易行的合成β-D-糖胺的方法，产率为70-80%。这些化合物为通过酰化1-氨基功能合成多种寡糖探针和衍生物提供了有价值的中间体。不同试剂对1-氨基功能的反应率不同。一般来说，与大的环系相互作用，如荧光基团丹磺酰氯和羧基荧光素，产物的产率为10%-20%，其中包括两种异构体的混合物，而较小的酰化试剂提供了所需的β-D-衍生物的接近定量的产率。立体效应可能解释了反应性的差异。在保持β-异构体构型的前提下，可以高产率地合成N-氯乙酰胺类化合物。随后，氯乙酰胺官能团的氨解得到相应的N-甘氨酰-β-衍生物。由此引入的连接体保留了氨基功能，具有固定的异构体构型、改进的稳定性和与各种试剂的均匀反应的有用性质，并且在结构上类似于天冬酰胺侧链。因此，存在为不同应用量身定做的低聚糖衍生物的产生潜力。
Incubation of reducing sugars in ammonium bicarbonate was found to be a simple procedure for the formation of beta-D-glycosylamines of purified complex oligosaccharides in 70-80% yield. These provide valuable intermediates for the synthesis of a wide range of oligosaccharide probes and derivatives by acylation of the 1-amino function. The 1-amino function showed different rates of reactivity with different reagents. In general, interactions with large ring systems such as the fluorophores dansyl chloride and carboxyfluorescein gave 10-20% yields of products, which consisted of mixtures of both anomeric forms, whereas smaller acylating reagents gave near-quantitative yields of the desired beta-D-derivatives. Steric effects may explain differences in reactivity. N-Chloroacetamido derivatives could be obtained in high yield with retention of the beta-anomeric configuration. Subsequent ammonolysis of the chloroacetamido function afforded the corresponding N-glycyl beta-derivatives. The linker thereby introduced retains the amino function, possesses the useful properties of fixed anomeric configuration, improved stability, and uniform reactivity with a variety of reagents, and is structurally analogous to an asparagine side chain. The potential therefore exists for the generation of oligosaccharide derivatives tailored for different applications.