Intramolecular Anodic Olefin Coupling Reactions

分子内阳极烯烃偶联反应

• 批准号: 1151121
• 负责人: William Buhro
• 金额: $ 45万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-08-15 至 2016-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1151121&HistoricalAwards=false
• 关键词: Intramolecular; Anodic; Olefin; Coupling; Reactions

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 will explore the chemistry of highly reactive radical cation intermediates and the molecular transformations that they trigger. The radical cation intermediates are generated electrochemically, a versatile technique that allows for structure-reactivity studies to be conducted on the radical cations. These studies serve to increase our mechanistic insight into the factors that control radical cation initiated reactions, and in so doing open up the opportunity to discover new synthetic methods for the construction of complex organic molecules. Since the electrochemical methods being developed can be conducted with the use of sunlight as the source of electricity, the chemistry holds great potential as a sustainable method. For example, chemical oxidation reactions utilize stoichiometric amounts of a chemical oxidant and in so doing require the formation of a stoichiometric reduction product as waste. In contrast, electrochemical oxidation reactions do not employ a chemical oxidant. Instead, the oxidation occurs by the loss of an electron to an anode surface. The required reduction reaction is channeled toward the formation of hydrogen gas at the cathode. Hence, a solar-driven electrochemical oxidation consumes only sunlight and generates hydrogen as the only byproduct. The proposed research will seek to expand this approach as a general synthetic method. Finally, this project will provide an excellent training environment for students, from pre-undergraduate to graduate, including those from historically underrepresented in the sciences.

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教授将探索高活性自由基阳离子中间体的化学及其引发的分子转化。自由基阳离子中间体是通过电化学产生的，这是一种通用的技术，允许对自由基阳离子进行结构-反应性研究。这些研究有助于增加我们对控制自由基阳离子引发反应的因素的机械洞察力，从而为发现构建复杂有机分子的新的合成方法打开了机会。由于正在开发的电化学方法可以利用阳光作为电力来源进行，因此化学作为一种可持续的方法具有巨大的潜力。例如，化学氧化反应利用化学计量的化学氧化剂，在这样做时，需要形成化学计量还原产物作为废物。相反，电化学氧化反应不使用化学氧化剂。相反，氧化是通过将一个电子损失到阳极表面来进行的。所需的还原反应被引导到阴极上形成氢气。因此，太阳能驱动的电化学氧化只消耗阳光，并产生氢气作为唯一的副产品。拟议的研究将寻求将这一方法扩展为一种通用的合成方法。最后，这个项目将为学生提供一个很好的培训环境，从预科到毕业，包括那些在科学界历史上代表性不足的学生。