Intramolecular Anodic Olefin Coupling Reactions

在这个由化学系化学合成项目资助的项目中，圣路易斯华盛顿大学化学系的Kevin Moeller教授正在探索电化学作为构建制药和化学工业经常感兴趣的复杂分子的工具的实用性。该方案有两个主要目标。首先是更好地了解高活性中间体，这些中间体对增加有机分子功能的合成反应至关重要。第二是建立更大的合成化学社区所需的化学洞察力，以充分利用电化学方法。这项工作的更广泛影响是科学和教育。 在科学前沿，电化学作为一种可持续技术具有巨大的潜力。这些反应可以以使用阳光（或任何其他清洁的电力来源）作为唯一能源的方式进行，并且不会产生废物。这样的过程既节省原子又节省能源。由于这些优点，电化学方法越来越受欢迎，来自世界各地的许多科学家都在招募Moeller教授来帮助他们自己利用这些反应。在教育方面，该项目支持年轻科学家在化学和电化学技术方面的培训，开发本科生实验室实验，让学生接触他们的第一次电化学反应，并继续实施利用动物园和科学中心教育计划向公众教授科学的推广活动。 该项目所追求的科学利用了机理研究，以指导新的自由基阳离子引发的环化反应的发展，并说明电化学方法如何用作合成工具。例如，最近的观察表明，从分子中除去第二个电子在成功的环化反应中起着关键作用，这一观察结果正被用于设计新的反应，这些反应利用第二个氧化步骤来驱动过程完成并提供独特的反应模式。与此同时，新的竞争研究正在被用来探索这些机制研究结果的一般性，以及设计新的方法来合成螺环。正在开发新的成对电化学方法，其利用在电化学反应中在两个电极处发生的反应，以使该过程的能量经济性最大化。对于更大的合成界来说，这些方法中的每一种都可以说明电化学方法的强大性。随着越来越多的合成化学家对他们自己设计的电化学反应产生兴趣，Moeller小组仍然准备帮助他们实现这些反应。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Kevin Moeller of the Department of Chemistry at Washington University in St. Louis is exploring the utility of electrochemistry as a tool for building the complex molecules that are frequently of interest to the pharmaceutical and chemical industries. The program has two main goals. The first is to gain a better understanding of the highly reactive intermediates central to synthetic reactions that increase the functionality of organic molecules. The second is to build the chemical insight necessary for the larger synthetic chemistry community to take full advantage of electrochemical methods. The broader impacts of the work are both scientific and educational. On the science front, the proposed electrochemistry holds great potential 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 no waste product. Such processes are both atom and energy economical. Because of these advantages, electrochemical methods are gaining in popularity, and numerous scientists from around the world enlist Professor Moeller to aide their own efforts to capitalize on the reactions. On the education front, the project supports 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 and science center educational programs to teach science to the general public. The science being pursued in this project capitalizes on mechanistic studies to both guide the development of new radical cation triggered cyclizations and illustrate how electrochemical methods can be used as synthetic tools. For example, recent observations that the removal of a second electron from a molecule plays a critical role in a successful cyclization reaction are being used to design new reactions that utilize this second oxidation step to both drive the processes to completion and to afford unique modes of reactivity. At the same time, new competition studies are being used to both probe the generality of these mechanistic findings, as well as to design new approaches to the synthesis of spirocyclic rings. New paired electrochemical methods, that take advantage of the reactions occurring at both electrodes in an electrochemical reaction, are being developed in order to maximize the energy economy of the processes. Each of these methods serves to illustrate, for the larger synthetic community, just how powerful electrochemical methods can be. As more synthetic chemists become interested in electrochemical reactions of their own design, the Moeller group remains poised to assist their efforts to implement them.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.