AMIDOGLYCOSYLATION REACTIONS OF GLYCAL AZIDOFORMATES

糖基叠氮甲酸酯的酰胺糖基化反应

• 批准号: 6224874
• 负责人: CHRISTIAN M. ROJAS
• 金额: $ 12.63万
• 依托单位: BARNARD COLLEGE
• 依托单位国家: 美国
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-03-01 至 2004-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6224874
• 关键词: aminosugar; azides; chemical synthesis; formates; glycosylation; nitrene; saturated /unsaturated bonds; stereochemistry

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.

描述：（主要研究者的摘要）将开发一种新方法 用于合成 2-氨基-2-脱氧糖，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 立体选择性过程，糖基叠氮甲酸酯将发生分子内 转化为酰基氮烯后碳-碳双键氮丙啶化。 将探索光解和金属催化途径来启动 氮烯的形成。由此产生的高反应性氮丙啶预计将 在二糖和寡糖的形成中作为原位糖基供体， 氮并入糖亚基的 C-2 位置。这 将使用一系列糖基来研究独特的合成序列 叠氮甲酸酯，由羰基咪唑化物通过温和的二烷基锡制备 氧化物促进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 几丁质酶抑制剂异糖脒的二-N-乙酰别糖胺部分， 强烈抑制昆虫生长的化合物，有潜力作为 物种选择性杀菌剂。此外，这项工作将扩展基础 叠氮甲酸酯和酰基氮烯反应性的知识。另一个重要的 该项目的结果将是让本科生参与各个方面 拟议的研究，鼓励巴纳德学院最优秀和最聪明的人 女性从事化学科学职业。