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

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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.