Collaborative Research: Electrochemical Ni-Catalyzed Reductive Biaryl Coupling: Mechanistic Studies to Enable Chemical Synthesis

合作研究：电化学镍催化还原联芳基偶联：实现化学合成的机理研究

• 批准号: 2154699
• 负责人: Robert Paton
• 金额: $ 18.01万
• 依托单位: Colorado State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-05-01 至 2025-04-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154699&HistoricalAwards=false
• 关键词: Collaborative; Research; Electrochemical; Ni; Catalyzed

With the support of the Chemical Catalysis program in the Division of Chemistry, a collaborative team including Daniel Weix and Shannon Stahl of the University of Wisconsin-Madison, Mohammad Rafiee of the University of Missouri-Kansas City, and Robert Paton of Colorado State University are studying new approaches toward the electrochemical synthesis of chemicals useful in polymers and agriculture. This collaborative project will use analytical and computational tools to shed light on how these reactions occur and what factors are important for success. The lessons learned will enable lower-cost, greener synthesis of important molecules using electricity in place of metal reductants. The research team will also work to improve equal representation in chemistry via several established Bridge and outreach programs. Finally, the team will teach the broader chemistry community about the new tools of organic electrochemistry through courses and short courses.This collaborative team from the University of Wisconsin-Madison, the University of Missouri-Kansas City, and Colorado State University is studying electrochemistry-driven nickel catalyzed reductive biaryl synthesis from a variety of aryl electrophiles. The research team will use a combination of stoichiometric organonickel studies, theory, and electroanalytical techniques to understand how each step in the biaryl synthesis (oxidative addition, transmetalation, reduction, and reductive elimination) is influenced by catalyst identity, conditions, and applied potential. This understanding will be used to drive further studies to improve catalyst turnover number, turnover frequency, and selectivity, including the development of cross-selective reactions, to make electrochemical reductive biaryl synthesis suitable for commercial scale-up in flow reactors. These studies will contribute to an improved understanding of nickel catalysis and electrosynthesis and the resulting reactions will be lower-cost, more green alternatives to the state-of-the-art biaryl syntheses that utilize unselective oxidation reactions, expensive precious metal catalysts, and reactive aryl nucleophiles.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.

在化学催化计划的支持下，包括威斯康星大学麦迪逊分校的Daniel Weix和Shannon Stahl在内的合作团队，密苏里 - 肯萨斯城市城市的Mohammad Rafiee以及科罗拉多州立大学的Robert Paton of Colorado State University正在研究对电化学合成的新方法。该协作项目将使用分析和计算工具来阐明这些反应的发生方式以及哪些因素对成功很重要。所学的经验教训将使用电力代替金属还原剂来实现重要分子的较低成本，更绿色的合成。研究团队还将通过几个既定的桥梁和外展计划来提高化学方面的平等代表。 Finally, the team will teach the broader chemistry community about the new tools of organic electrochemistry through courses and short courses.This collaborative team from the University of Wisconsin-Madison, the University of Missouri-Kansas City, and Colorado State University is studying electrochemistry-driven nickel catalyzed reductive biaryl synthesis from a variety of aryl electrophiles.研究小组将结合结合化学计量的器官研究，理论和电分析技术，以了解如何在催化剂，条件，条件和应用潜力的情况下影响双疗法合成中的每个步骤（氧化添加，跨金属化，还原，还原和还原消除）。这种理解将用于推动进一步的研究，以提高催化剂的周转率，周转频率和选择性，包​​括跨选择性反应的发展，以使电化学还原性双biaryl合成适用于流量反应堆中的商业规模。这些研究将有助于改善对镍催化和电合合成的了解，而所得反应将是较低的成本，更绿色的替代品，与最先进的双型物质合成特征相比，利用非选择性的氧化反应，昂贵的珍贵金属催化剂和反应性芳基的促进型促进型的促进性，并且已经反映了NSF的构建，并且已经反映了nsf的宣传。和更广泛的影响审查标准。