CAREER: Stereocontrolled Synthesis of 1,2-cis Glycosides

这个研究项目建立在一个前所未有的O-2/O-5在低聚糖和糖缀合物合成中的协同效应的发现。将探讨糖基化反应的新方面和影响其立体选择性的因素。主要目的包括研究糖基化协同效应的机理，探索其在立体控制糖基化中的应用。生物有机化学和碳水化合物化学将作为化学课程和各级各种推广活动的中心组成部分。这些活动包括开发和实施新的有机化学课程，改进实验课程，以及建立定期的专题讨论会。在有机和大分子化学项目的CAREER奖的支持下，密苏里大学圣路易斯分校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）单位的有机分子的新方法。碳水化合物参与许多人类疾病发病机制的阐明是困难的，因为相关的天然碳水化合物分子的复杂性和相对较低的可用性。低聚糖与其他天然生物聚合物、蛋白质和DNA之间的主要概念区别在于糖-糖键的性质，它代表了一个需要三维结构控制的新位点。形成这种具有完全结构控制的“糖苷”键的必要性是低聚糖仍然是21世纪最重大的合成挑战之一的主要原因。Demchenko教授还将开发和实施新的有机化学课程，并振兴实验室课程，纳入生物有机和碳水化合物化学的中心主题，并将建立专门针对糖科学的定期专题讨论会。

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.