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

在化学系化学催化项目的支持下，一个由威斯康星大学麦迪逊分校的Daniel Weix和Shannon Stahl、密苏里大学堪萨斯城分校的Mohammad Rafiee和科罗拉多州立大学的Robert Paton组成的合作团队正在研究聚合物和农业中有用的化学物质的电化学合成的新方法。这个合作项目将使用分析和计算工具来阐明这些反应是如何发生的，以及哪些因素对成功很重要。吸取的经验教训将使用电取代金属还原剂合成重要分子的成本更低、更环保。研究小组还将通过几个已建立的桥梁和外展项目，努力提高化学领域的平等代表性。最后，该团队将通过课程和短期课程向更广泛的化学社区教授有机电化学的新工具。这个来自威斯康星大学麦迪逊分校、密苏里大学堪萨斯城分校和科罗拉多州立大学的合作团队正在研究电化学驱动的镍催化从各种芳基亲电试剂中还原双芳基合成。研究小组将结合有机镍的化学计量学研究、理论和电分析技术来了解联芳基合成的每个步骤（氧化加成、金属转化、还原和还原消除）是如何受到催化剂特性、条件和应用潜力的影响的。这一认识将用于推动进一步的研究，以提高催化剂的周转次数、周转频率和选择性，包括交叉选择反应的发展，使电化学还原性联芳基合成适合于流动反应器的商业规模。这些研究将有助于提高对镍催化和电合成的理解，由此产生的反应将是成本更低、更环保的替代最先进的联芳基合成，这些联芳基合成利用非选择性氧化反应、昂贵的贵金属催化剂和活性芳基亲核试剂。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.