RUI: Reaction Acceleration, Mediation, and Catalysis by In Situ Silylation

在这个由化学部门化学合成项目资助的项目中，里士满大学化学系的Chiles W. Downey教授将探索使用硅化剂加速、调解和催化一系列化学反应。硅基化剂，如三甲基硅基三氟甲烷磺酸盐，将起到两种作用。首先，亲电硅中心将作为路易斯酸激活其他亲电试剂向亲核攻击。其次，强硅-氧键或其他硅-杂原子键的形成将有助于推动这些化学反应的完成，从而提供高产量和更短的反应时间。特别令人感兴趣的是羧酸的α取代反应，这类反应通常受到强碱反应条件的阻碍。当使用这些反应物时，硅烷化剂可以通过将酸官能团转化为更容易控制的硅烷酯来发挥第三种作用。这项工作可能导致羧酸的不对称反应的发展，如不对称羧酸醛醇反应。该项目对基础生物科学、制药和农业工业具有重大影响，因为它将直接提供对生物合成和化学合成具有强大生物活性的复杂分子至关重要的手性羧酸盐构建块的途径。强调一锅反应减少了废物的产生，提供了积极的环境影响，并节省了时间和经济。该项目还为本科研究生提供培训，为从事科学、卫生领域和学术界的职业做准备。在这个奖项的过程中，除了在常规学年进行的实验外，还将资助六到八名研究人员进行为期十周的密集夏季研究体验。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Chiles W. Downey of the Department of Chemistry at the University of Richmond will explore the use of silylating agents for the acceleration, mediation, and catalysis of an array of chemical reactions. Silylating agents such as trimethylsilyl trifluoromethanesulfonate will act in two roles. First, the eletrophilic silicon center will act as a Lewis acid to activate other electrophiles toward nucleophilic attack. Second, the formation of strong silicon-oxygen or other silicon-heteroatom bonds will help drive these chemical reactions to completion, affording high yields and shorter reaction times. Of particular interest are alpha-substitution reactions of carboxylic acids, a class of reactions commonly hampered by strongly basic reaction conditions. When these reactants are employed, the silylating agent can play a third role by transforming the acid functional group into a more easily controllable silyl ester. This work could lead to the development of asymmetric reactions of carboxylic acids, such as an asymmetric carboxylic acid aldol reaction. This project has significant impacts on fundamental biological sciences, pharmaceutical and agricultural industries, as it would provide direct access to chiral carboxylate building blocks important in the biosynthesis and chemical synthesis of complex molecules of potent biological activities. The emphasis upon one-pot reactivity reduces the generation of waste, providing a positive environmental impact as well as savings with respect to time and economics. The project also provides trainings for undergraduate research students in preparation for careers in the science health fields as well as academia. Over the course of this award, six to eight researchers will be funded for an intensive ten-week summer research experience in addition to experiments carried out during the regular academic year.