Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

• 批准号: 1463913
• 负责人: Kevin Moeller
• 金额: $ 46.5万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-08-01 至 2019-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1463913&HistoricalAwards=false
• 关键词: Intramolecular; Anodic; Olefin; Coupling; Reactions

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.

通过这一奖项，化学系的化学合成项目资助了圣路易斯华盛顿大学化学系的凯文·莫勒教授，他将利用电化学方法探测高活性中间体，这些中间体是合成反应的核心，可以增加有机分子的功能。这项工作旨在为设计新的、更有效的合成途径，以获得制药和化学工业感兴趣的分子，并开发电化学作为实现这些转化的可持续工具奠定基础。这项工作的更广泛的影响是科学和教育。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。这种反应可以用阳光（或任何其他清洁的电力来源）作为唯一的能量来源，并产生氢气作为唯一的副产品。出于这个原因，来自世界各地的科学家们请莫勒教授帮助他们自己努力利用电化学方法。在教育方面，该项目将支持培养化学和电化学技术方面的年轻科学家，发展本科生实验室实验，让学生接触到他们的第一次电化学反应，并继续实施利用动物园教育项目向公众传授科学的推广活动。在这个项目中所追求的特定科学利用了竞争研究和循环伏安法的结合，以探索新的自由基阳离子触发环化的机制基础。机械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。电化学的应用使机械研究和合成研究都受益匪浅。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活性自由基阳离子。这使得Moeller小组能够系统地改变自由基阳离子的结构，然后探索这些变化如何改变中间体的化学反应性。同样的技术被用于进行可扩展的合成反应，这一努力证明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。