Mechanism and Discovery of Metal-Catalyzed Fluoroalkylation Reactions

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The Chemical Catalysis Program of the Chemistry Division supports the project by Professor John F. Hartwig in the Department of Chemistry at the University of California, Berkeley to improve catalytic processes that form organic molecules containing fluorine atoms. These studies are important because fluorinated organic molecules are vital to material, agricultural, and medicinal sciences. For example, over 30% of new pharmaceuticals and 25% of licensed herbicides contain fluorine. This project answers a series of questions to understand how these catalytic systems work. This knowledge is then being used to design solutions to overcome catalytic bottlenecks that will increase the availability of fluorinated organic molecules. The program also includes outreach activities for K-12 students on chemical catalysis topics, short training courses for the chemical workforce, and presentations to general audiences to reach future scientists from underrepresented groups.Although a large fraction of pharmaceuticals and agrochemicals contain fluorine, available fluorinated molecules are largely limited to those derived from simple fluoroarenes, trifluoromethylarenes, or trifluoroacetates. In order to reliably synthesize molecules with fluoroalkyl groups, new ways to induce and control the reactivity of fluoroalkyl transition-metal complexes in catalytic processes are needed. These studies are improving catalytic capabilities for forming fluorinated organic compounds by preparing fluoroalkyl complexes of palladium and fluoroallylic complexes of iridium and determining the factors that promote carbon-carbon bond formation with these intermediates. This fundamental work is revealing how to turnover catalytic processes involving these transition metal intermediates to advance the synthesis of fluorinated organic molecules. In addition, these studies are determining how to control the formation of stereogenic centers and how to tolerate a larger array of functional groups. This project is impacting the catalytic synthesis of molecules that are important in materials science, medicinal chemistry, and agroscience. Simultaneously, this program is providing training for a diverse group of graduate and undergraduate students, as well as outreach activities to K-12 students to motivate the next generation of scientists.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.