AMIDOGLYCOSYLATION REACTIONS OF GLYCAL AZIDOFORMATES

描述：（主要研究者摘要）将开发一种新方法 对于2-氨基-2-脱氧糖的合成，一类化合物包括 许多生物学和医学上重要的物质。在一个高度 在立体选择性过程中，糖基叠氮甲酸酯将进行分子内 在转化为酰基氮烯时发生碳-碳双键氮丙啶化。 将探索光解和金属催化途径， 氮烯形成。预期所得的高反应性氮杂环丙烷 在二糖和寡糖的形成中作为原位糖基供体， 在糖亚基的C-2位掺入氮。这 独特的合成序列将使用一系列的糖基化合物进行研究。 叠氮基甲酸酯，由羰基咪唑通过温和的二烷基锡 氧化物促进的与三甲基甲硅烷基叠氮化物的反应。拟议的研究将 扩大可用于化学制备的合成工具的范围， 具有生物学意义的2-氨基糖，包括 几丁质酶抑制剂阿洛酰胺的二-N-乙酰阿洛胺部分， 这种化合物能强烈抑制昆虫的生长， 物种选择性杀真菌剂。此外，这项工作将扩大基本的 叠氮甲酸酯和酰基氮烯反应性知识。另一个重要 该项目的结果将涉及本科生在各个方面 这项研究计划鼓励巴纳德学院最优秀和最聪明的学生 妇女从事化学科学的职业。

DESCRIPTION: (Principal Investigator's Abstract) A new method will be developed for the synthesis of 2-amino-2-deoxy sugars, a class of compounds that includes many biologically and medicinally important substances. In a highly stereoselective process, glycal azidoformates will undergo intramolecular carbon-carbon double bond aziridination upon conversion to the acyl nitrenes. Both photolytic and metal-catalyzed pathways will be explored to initiate nitrene formation. The resulting highly reactive aziridines are expected to serve as in situ glycosyl donors in the formation of di- and oligosaccharides, with nitrogen incorporated at the C-2 position of the sugar subunits. This unique synthetic sequence will be investigated using a range of glycal azidoformates, prepared from the carbonyl imidazolides via a mild, dialkyltin oxide-promoted reaction with trirnethylsilyl azide. The proposed studies will enlarge the array of synthetic tools available for the chemical preparation of biologically significant 2-aminosaccharides, including the di-N-acetylallosamine portion of the chitinase inhibitor allosamidin, a compound that strongly curtails insect growth and has potential as a species-selective fungicide. In addition, this work will extend fundamental knowledge of azidoformate and acyl nitrene reactivity. Another important outcome of the project will be to involve undergraduate students in all facets of the proposed research, encouraging Barnard College's best and brightest women to pursue careers in the chemical sciences.