Mechanism-based development of new nickel-catalyzed stereospecific cross-electrophile coupling reactions of sulfonamides

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With this award, the Chemical Synthesis Program of the Division of Chemistry supports the research of Professor Elizabeth Jarvo in the Department of Chemistry of the University of California, Irvine. Professor Jarvo is developing new ways to make carbon-containing molecules used in agriculture, pharmaceuticals, polymers and other materials. Traditional methods of making these molecules rely on precious metals that are limited in supply and thus, expensive and sometimes hard to obtain. Dr. Jarvo is trying to replace those metals with more earth abundant nickel-based reagents that would be more environmentally sustainable. With a focus on how the reaction occurs, the Jarvo laboratory is gaining new insight into carbon-carbon bond forming reactions that are important industrially. This project provides hands-on training to graduate and undergraduate students. Professor Jarvo also organizes career-development workshops that target female and underrepresented faculty and graduate students. She co-organizes a day-long research symposium for Southern California undergraduate students and participates in outreach programs that connect the UC Irvine campus to nearby underserved middle schools.Professor Elizabeth Jarvo is developing stereospecific cross-coupling and cross-electrophile coupling reactions of benzylic sulfonamides using nickel catalysts. These new, catalytic methods enable the synthesis of complex biologically active molecules. For example, the work is defining stereoselective strategies for the synthesis of cyclopropanes, a privileged moiety in medicinal chemistry. Importantly, mechanistic experiments clarify the factors that govern reactivity of organonickel complexes to favor two-electron reactions versus single-electron reactions, a long-standing challenge in development of nickel-catalyzed reactions. Structural characterization of organonickel intermediates provides experimental evidence for the oxidation state of key catalytic intermediates and facilitates the design of new catalysts.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.