CAS: Catalytic sp3 Carbon-Hydrogen (C-H) Functionalization with Earth Abundant Metals

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Timothy Warren of the Department of Chemistry at Georgetown University to develop sustainable catalysts that link abundant chemical building blocks. Using catalysts to link molecular fragments by the formation of new carbon-carbon, carbon-nitrogen, and carbon-oxygen bonds usually requires multi-step chemical processes to first activate the molecular fragments so that they are more reactive. Professor Warren and his team of graduate and undergraduate researchers are designing new ways to connect chemical building blocks using carbon-hydrogen bonds that are difficult to break but found in most feedstock chemicals. The catalysts that are being developed for these reactions are derived from earth abundant copper. These studies involve experiments designed to gain fundamental insight into how the catalysts work to be able to improve their performance in the advanced manufacture of industrial chemicals. This project is providing training for a diverse group of students. Dr. Warren and his group introduce the general public to chemistry at the biannual USA Science and Engineering Festival in Washington, DC. The team will continue to work with young scientists at the beginning of their scientific careers. Each summer a high school student will gain valuable experience and access to a range of more experienced scientists (undergrads, grads, PI) while contributing to the chemical enterprise. Finally, Professor Warren and his students will also provide day-long, hands-on laboratory experiences each summer for rising high school seniors from the Cristo Rey and KIPP networks that serve underprivileged, low-income, and diverse student populations that illustrate connections between Chemistry and the Environment. Catalytic reactions for the conversion of carbon-hydrogen (C-H) bonds in abundant chemical feedstocks to value-added carbon-nitrogen (C-N), carbon-oxygen (C-O), and carbon-carbon (C-C) bonds are valuable for improving the efficiency of synthetic processes. These transformations bypass the steps required to activate reagents and simultaneously decrease waste. Professor Warren and his research group have discovered that a copper-catalyzed radical relay reaction can be used to functionalize C-H bonds and they are currently investigating new synthetic transformations that can be achieved with this catalytic system. These studies involve optimizing the catalyst to accommodate new types of reagents to react with the C-H bonds, exploring new oxidants to decrease the excess amount of alkane currently required, and investigating asymmetric systems for C-H amidation. In addition, fundamental mechanistic studies are being performed to collect information that will facilitate further development and optimization. These research activities also serve as a training ground for a diverse group of graduate, undergraduate, and high school students. 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.