Radical Migration Reactions Driven by Sustainable Transition-Metal Catalysis

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With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Ming-Yu Ngai of Purdue University will study first-row transition metals in catalysis to establish new chemical processes and foster sustainable practices. This project aims to harness the reactivity of earth-abundant cobalt and nickel catalysts to develop new methods to functionalize carbohydrates and other important small molecule building blocks. The project seeks to both further understanding of the fundamental reactivity and mechanisms in these processes as well as develop new reactions to facilitate access to molecular scaffolds with potential societal impacts. Through collaboration with the College of Science K-12 Outreach team at Purdue, the project also seeks to inspire high school students by introducing them to sustainable catalysis concepts, highlighting chemistry's role in solving global challenges and promoting sustainability. By contributing to the scientific understanding of complex radical migration-related mechanisms, these studies have the potential to catalyze the development of related sustainable methodologies in organic synthesis.Under this award, Professor Ngai and his research team will explore the integration of ground-state metalloradical properties of cobalt and nickel complexes with 1,2-radical migration (RaM) reactivity. The project is set to unveil novel pathways for the site- and stereoselective functionalization of carbohydrates—a significant challenge in carbohydrate chemistry—and to broaden the reaction scope of allyl carboxylates. Through a combination of experimental and computational studies, the team aims to develop a catalytic platform that provides for axial and equatorial selectivity of the C2-arylation reaction. These investigations are expected to provide new insights into radical migratory cross-coupling reactions mediated by nickel and cobalt catalysts, and in so doing contribute to advances in radical chemistry and sustainable catalytic processes.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.