Stereoselective synthesis of α- and β-glycosylamide derivatives from glycopyranosyl azides via isoxazoline intermediates
Stereoselective synthesis of α- and β-glycosylamide derivatives from glycopyranosyl azides via isoxazoline intermediates
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DOI：
10.1021/ja028694u
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发表时间：
2003-04-16
影响因子：
15
通讯作者：
DeShong, P
中科院分区：
文献类型：
--
作者：
Damkaci, F;DeShong, P
用Ph 3 P处理2-乙酰氧基吡喃葡萄糖基叠氮化物，通过磷亚胺的闭环得到异恶唑啉。原位生成的异恶唑啉与酰化试剂偶联得到α-或β-吡喃葡萄糖酰胺的混合物。α/β比值取决于所用的酰化试剂和金属盐。例如，在CuCl 2存在下，异恶唑啉3与Z-Asp-（SPy）-OBn偶联仅产生α-N-吡喃葡萄糖基天冬酰胺衍生物8。这一通用程序已被应用于单糖、二糖和三糖体系。
Treatment of 2-acetoxy glycopyranosyl azides with Ph3P gave isoxazolines by ring closure of the phosphorimine. Coupling of in situ generated isoxazolines with acylating reagents gave mixtures of α- or β-glycopyranosyl amides. The α/β ratio depended upon the acylating reagent and metal salts employed. For example, coupling of isoxazoline3with Z-Asp-(SPy)-OBn in the presence of CuCl2gave exclusively α-N-glucopyranosylasparagine derivative8. This general procedure has been applied to mono-, di-, and trisaccharide systems.