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NSF化学部的化学合成计划的支持下，匹兹堡大学的Paul Floreancig教授使用电化学来合成复杂的有机化合物。电化学反应使用电流代替传统化学物质。化学试剂通常会产生不希望的副产物，因为它们产生的能量过多或无法产生（或破坏）特定的化学键。由于可以在给定电势（电压）上精确控制电流，因此可以调整电化学反应以提供所需转换所需的适当能量。通过这种方式，与传统的化学反应相比，电化学反应有望减少化学废物。这项研究使用电化学技术产生了新的环境良性合成方法。研究小组与合作者合作，将有机反应发展与理论和电化学技术相结合。新方法开发说明了在增加分子复杂性中采用氧化反应的力量。研究小组对追求绿色化学的坚决承诺，通过这项研究学到的教训被用作针对环境良性有机综合的本科班级的例子。该项目使用电化学氧化来推进FloreAncig组开发的氧化碳 - 氢键裂解过程。该研究取代了用oxoammonium离子用作化学计量试剂的奎因酮氧化剂。与喹酮酮相比，黄兆离子更容易通过阳极氧化再生，并提供了其他优势，例如更容易的反应性调整以及为映选择性合成而开发不对称变体的潜力。第一个目的是优化氧化环化反应中黄兆离子的电化学再生，从而通过探索氧化强度，电极材料和底物氧化潜力的影响来允许低催化剂载荷。第二个目标是深入了解oxoammonium离子通过联合实验和理论方法通过氧化碳 - 氢键裂解的机理细微差异，该方法提供了有关过渡状态电荷转移和几何形状的重要性的信息。第三个目标是开发出使用oxoammonium离子而不是奎因酮的新变化，包括环加成反应和动力学分辨率。通过通过出版和研讨会来传播结果，FloreAncig小组为科学界提供了有力的新转变，有价值的机理见解和蓝图，用于将电化学与氧化功能反应相互接触。该奖项反映了NSF的法定任务，并通过评估了基金会的范围来反映支持者的法定任务，并通过基金会的范围进行了评估。