Intramolecular Anodic Olefin Coupling Reactions

该奖项由化学系化学合成计划资助圣路易斯华盛顿大学化学系的Kevin Moeller教授使用电化学方法探索合成反应中的高活性中间体，以增加有机分子的官能度。这一努力旨在为设计新的、更有效的合成途径来获得制药和化学工业感兴趣的分子奠定基础，并将电化学发展为实现这些转变的可持续工具。这项工作的更广泛影响既是科学的，也是教育的。在科学方面，这个项目向其他人展示了电化学作为一种可持续技术的整体效用。这些反应可以以利用阳光(或任何其他清洁电力来源)作为唯一能源，并产生氢气作为唯一副产品的方式进行。出于这个原因，来自世界各地的科学家邀请默勒教授帮助他们自己利用电化学方法的努力。在教育方面，该项目将支持对年轻科学家进行化学和电化学技术方面的培训，开发使学生接触到他们第一次电化学反应的本科实验室实验，并继续实施利用动物园教育计划向普通公众教授科学的外联活动。这个项目所追求的具体科学结合了竞争研究和循环伏安法，以探索新的自由基阳离子引发环化的机理基础。机械论的洞察力被用来开发新的合成方法，展示如何最好地利用反应。电化学的使用对机理研究和合成研究都大有裨益。电化学方法允许在几乎相同的反应条件下从各种各样的底物中生成反应性自由基阳离子。这使得Moeller小组能够对自由基阳离子的结构进行系统的改变，然后探索这些变化如何改变中间体的化学反应活性。同样的技术也被用于进行可扩展的合成反应，这一努力展示了电化学的合成效用，并有望引起合成界其他人对电化学方法的兴趣。

With this award, the Chemical Synthesis Program in the Division of Chemistry is funding Professor Kevin Moeller of the Department of Chemistry at Washington University in St. Louis to use electrochemical methods to probe the highly reactive intermediates central to synthetic reactions that increase the functionality of organic molecules. The effort serves to build a foundation for the design of new, more efficient synthetic routes to molecules of interest to the pharmaceutical and chemical industries and to develop electrochemistry as a sustainable tool for accomplishing those transformations. The broader impacts of the work are both scientific and educational. On the science front, this project illustrates for others the overall utility of electrochemistry as a sustainable technique. The reactions can be run in a manner that uses sunlight (or any other clean source of electricity) as the only source of energy and generates hydrogen gas as the only byproduct. For this reason, scientists from around the world enlist Professor Moeller to aid their own efforts to capitalize on electrochemical methods. On the education front, the project will support the training of young scientists in both chemical and electrochemical techniques, the development of undergraduate laboratory experiments that expose students to their first electrochemical reactions, and the continued implementation of outreach activities that utilize zoo educational programs to teach science to the general public. The specific science being pursued in this project capitalizes on a combination of competition studies and cyclic voltammetry to probe the mechanistic underpinnings of new radical cation-triggered cyclizations. The mechanistic insight is used to develop new synthetic methods that demonstrate how to best take advantage of the reactions. Both the mechanistic and synthetic studies benefit greatly from the use of electrochemistry. Electrochemical methods allow for generation of the reactive radical cations from a wide variety of substrates with nearly identical reaction conditions. This enables the Moeller group to make systematic changes to the structure of a radical cation and then probe how those changes alter the chemical reactivity of the intermediate. The same technique is employed to conduct scalable synthetic reactions, an effort that demonstrates the synthetic utility of electrochemistry and one that is expected to generate interest in electrochemical methods by others in the synthetic community.