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Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

基本信息

批准号：
1764449
负责人：
Kevin Moeller
金额：
$ 48万
依托单位：
Washington University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-09-01 至 2022-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764449&HistoricalAwards=false
关键词：
Intramolecular Anodic Olefin Coupling Reactions

项目摘要

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.

在这个由化学系化学合成计划资助的项目中，圣路易斯华盛顿大学化学系的Kevin Moeller教授正在探索将电化学作为一种工具来构建制药和化工行业经常感兴趣的复杂分子。该计划有两个主要目标。第一个是更好地了解高活性中间体，这些中间体是提高有机分子官能度的合成反应的核心。第二是为更大的合成化学界充分利用电化学方法建立必要的化学洞察力。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，拟议的电化学作为一种可持续的技术具有巨大的潜力。这些反应可以以利用阳光(或任何其他清洁电力来源)作为唯一能源的方式进行，并且不会产生废物。这样的过程既节约了原子，又节约了能源。由于这些优势，电化学方法越来越受欢迎，来自世界各地的许多科学家聘请默勒教授协助他们利用这些反应的努力。在教育方面，该项目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和科学中心教育计划向普通公众教授科学的外联活动。这个项目所追求的科学是利用机理研究来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，最近观察到的从分子中移除第二个电子在成功的环化反应中起着关键作用的观察正在被用来设计新的反应，这些反应利用第二步氧化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发现的普遍性，以及设计合成螺环的新方法。正在开发新的成对电化学方法，这种方法利用电化学反应中在两个电极上发生的反应，以最大限度地提高工艺的能量经济性。这些方法中的每一种，对于更大的合成社区来说，都是为了说明电化学方法可以有多强大。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感兴趣，默勒团队仍然准备帮助他们努力实施这些反应。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。