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Applications of Oxoammonium Salts to Green Organic Reactions

氧铵盐在绿色有机反应中的应用

基本信息

批准号：
1855877
负责人：
Paul Floreancig
金额：
$ 48.62万
依托单位：
University of Pittsburgh
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-09-01 至 2022-08-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1855877&HistoricalAwards=false
关键词：
Applications Oxoammonium Salts Green Organic

项目摘要

Supported by the Chemical Synthesis Program in the NSF Division of Chemistry, Professor Paul Floreancig at the University of Pittsburgh uses electrochemistry to the synthesize complex organic compounds. Electrochemical reactions use electrical currents in place of traditional chemicals. Chemical reagents often produce undesired by-products because they produce too much or too little energy to make (or break) specific chemical bonds; Because electrical currents can be precisely controlled at a given potential (voltage), electrochemical reactions can be tuned to provide just the right amount of energy needed for a desired transformation. In this way, electrochemical reactions promise to reduce chemical waste when compared to traditional chemical reactions. This research produces new environmentally benign synthetic methods using electrochemical techniques. The research team works with collaborators to combine organic reaction development with theory and electrochemical techniques. The new method development illustrate the power of employing oxidation reactions in increasing molecular complexity. The research team has a strong commitment to pursuing green chemistry and lessons learned through this research are used as examples in undergraduate classes directed toward environmentally benign organic synthesis. This project uses electrochemical oxidations to advance the oxidative carbon-hydrogen bond cleavage processes that have been developed in the Floreancig group. The study replaces quinone oxidants, which were originally used as stoichiometric reagents, with oxoammonium ions. The oxoammonium ions are more readily regenerated through anodic oxidation than their quinone counterparts and offer additional advantages, such as easier reactivity tuning and the potential for developing asymmetric variants for enantioselective synthesis. The first objective is to optimize the electrochemical regeneration of oxoammonium ions in oxidative cyclization reactions to allow for low catalyst loading by exploring the impact of oxidant strength, electrode material, and substrate oxidation potential. The second objective is to gain insight into the mechanistic nuances of oxidative carbon-hydrogen bond cleavage by oxoammonium ions through a combined experimental and theoretical approach that provides information on the importance of charge transfer and geometry of the transition states. The third objective is to develop new transformations that are possible with oxoammonium ions but not quinones, including cycloaddition reactions and kinetic resolutions. By disseminating the results through publication and seminars, the Floreancig group provides the scientific community with powerful new transformations, valuable mechanistic insights, and blueprints for interfacing electrochemistry with oxidative functionalization reactions.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.

在美国国家科学基金会化学部化学合成计划的支持下，匹兹堡大学的保罗·弗洛雷西格教授利用电化学来合成复杂的有机化合物。电化学反应用电流代替传统的化学物质。化学试剂通常会产生不受欢迎的副产品，因为它们产生的能量太多或太少，无法形成(或打破)特定的化学键；由于电流可以精确地控制在给定的电位(电压)下，电化学反应可以进行调节，以提供所需转换所需的适量能量。这样，与传统的化学反应相比，电化学反应有望减少化学废物。这项研究利用电化学技术产生了新的环境友好的合成方法。研究团队与合作者合作，将有机反应开发与理论和电化学技术结合起来。新方法的发展说明了利用氧化反应增加分子复杂性的力量。研究团队坚定地致力于追求绿色化学，通过这项研究获得的经验教训被用作环境友好型有机合成的本科生课堂上的范例。该项目使用电化学氧化来推进Floreancig小组开发的氧化碳氢键断裂过程。这项研究用氧铵离子取代了原来用作化学计量试剂的苯醌氧化剂。与对苯二酚相比，氧代铵离子更容易通过阳极氧化再生，并提供了额外的优点，例如更容易的反应调节和开发不对称变体用于对映体选择性合成的可能性。第一个目标是通过考察氧化剂强度、电极材料和底物氧化电位的影响，优化氧化环化反应中氧铵离子的电化学再生，以允许较低的催化剂负载量。第二个目标是通过实验和理论相结合的方法，深入了解氧铵离子氧化碳氢键断裂的机理细微差别，提供关于电荷转移和过渡态几何形状的信息。第三个目标是开发新的转化，包括环加成反应和动力学拆分，这些转化可以与氧铵离子进行，但不能与苯二酚发生。通过出版和研讨会，Floreancig小组为科学界提供了强大的新转变、有价值的机械学见解和将电化学与氧化官能化反应相结合的蓝图。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。