AMIDOGLYCOSYLATION REACTIONS OF GLYCAL AZIDOFORMATES

描述：(首席调查人员摘要)将开发一种新方法 为了合成2-氨基-2-脱氧糖，一类化合物包括 许多生物和医学上重要的物质。在一种高度的 立体选择过程，甘氨酸叠氮甲酸酯将经历分子内 碳-碳双键在转化为酰基硝烷时发生氮杂化反应。 将探索光解和金属催化的途径来引发 氮化物的形成。由此产生的高活性氮杂环丙烷有望 在二糖和寡糖的形成中充当原位糖基供体， 其中氮结合在糖亚单位的C-2位。这 将使用一系列甘氨酸对独特的合成序列进行研究 叠氮甲酸酯，由羰基咪唑通过温和的二烷基锡制得 氧化物促进的与三乙基叠氮硅的反应。拟议的研究将 扩大可用于化学制备的合成工具的范围 具有生物意义的2-氨基糖，包括 几丁质酶抑制剂别沙米丁的二-N-乙酰别三胺部分，a 一种强烈抑制昆虫生长的化合物，具有潜在的 物种选择性杀菌剂。此外，这项工作将从根本上扩展 叠氮甲酸盐和酰基硝酸酯的反应性知识。另一项重要的 该项目的结果将是让本科生在各个方面都参与进来 建议的研究，鼓励巴纳德学院最优秀和最聪明的 妇女从事化学科学方面的职业。

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.