CAREER: Stereocontrolled Synthesis of 1,2-cis Glycosides

职业：1,2-顺式糖苷的立体控制合成

• 批准号: 0547566
• 负责人: Alexei Demchenko
• 金额: $ 55.2万
• 依托单位: University of Missouri-Saint Louis
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-01-01 至 2011-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0547566&HistoricalAwards=false
• 关键词: CAREER; Stereocontrolled; Synthesis; cis; Glycosides

This research project builds from the discovery of an unprecedented O-2/O-5 cooperative effect in the synthesis of oligosaccharides and glycoconjugates. Novel aspects of the glycosylation reaction and factors affecting its stereoselectivity will be explored. Major aims include the investigation of the mechanistic aspects of the cooperative effect in glycosylation and exploration of its application in stereocontrolled glycosylations. Bioorganic and carbohydrate chemistry will be incorporated as central components in the chemistry curriculum and in a variety of outreach activities at all levels. These activities include development and implementation of new organic chemistry courses, improvement of the laboratory curriculum, and establishment of regular symposia dedicated to glycosciences.With the support of this CAREER award from the Organic and Macromolecular Chemistry Program, Professor Alexei V. Demchenko, of the Department of Chemistry and Biochemistry at the University of Missouri at St. Louis, is developing new methods for the synthesis of organic molecules containing carbohydrate (sugar) units. Elucidation of the mechanisms of carbohydrate involvement in the pathogenesis of many human diseases is made difficult by the complexity and relatively low availability of relevant natural carbohydrate-based molecules. The main conceptual difference between oligosaccharides and other natural biopolymers, proteins and DNA, is in the nature of the sugar-sugar bond, which represents a new site requiring three-dimensional control of structure. The necessity to form such "glycosidic" linkages with complete structural control is a primary reason oligosaccharides remain amongst the most significant synthetic challenges of the 21st century. Professor Demchenko will also develop and implement new organic chemistry courses and revitalize the laboratory curriculum, incorporating central themes from bioorganic and carbohydrate chemistry, and will establish regular symposia dedicated to glycosciences.

该研究项目建立在发现了一种前所未有的O-2/O-5协同作用在寡糖和糖缀合物的合成。糖基化反应的新方面和影响其立体选择性的因素将进行探讨。主要目的包括糖基化反应中协同效应的机理研究及其在立体控制糖基化反应中的应用。生物有机和碳水化合物化学将作为中心组成部分纳入化学课程和各级各种外联活动。这些活动包括开发和实施新的有机化学课程，改进实验室课程，并建立定期的专题讨论会，致力于糖科学。在有机和大分子化学计划的支持下，圣路易斯密苏里州大学化学和生物化学系的Alexei V. Demchenko教授，正在开发合成含有碳水化合物（糖）单元的有机分子的新方法。由于相关天然碳水化合物分子的复杂性和相对低的可用性，使得阐明碳水化合物参与许多人类疾病发病机制变得困难。寡糖与其他天然生物聚合物、蛋白质和DNA之间的主要概念差异在于糖-糖键的性质，糖-糖键代表了需要三维结构控制的新位点。形成具有完全结构控制的这种“糖苷”键的必要性是寡糖仍然是世纪最重要的合成挑战之一的主要原因。教授Demchenko还将开发和实施新的有机化学课程，振兴实验室课程，纳入生物有机和碳水化合物化学的中心主题，并将建立专门的糖科学定期研讨会。