CAREER: Reductive Carboxylation of Unsaturated Hydrocarbons

West Virginia University Research Corporation, Morgantown WV

Investigators

Abstract

With this CAREER Award from the Chemical Catalysis Program in the Chemistry Division, Professor Brian Popp at West Virginia University (WVU) is developing new catalytic methods that utilize carbon dioxide (CO2) in chemical synthesis. CO2 is an undervalued and underutilized chemical raw material. This project is focusing on reactions of CO2 to prepare important chemicals useful for the manufacture of pharmaceuticals, agrochemicals, and materials. Professor Popp's research is using both experimental and computational methods to better understand how these reactions work and how to improve them. Professor Popp is pursuing educational activities aimed at increasing the quality and quantity of U.S. scientists, especially from underrepresented groups served by WVU. This is being accomplished by enhancing the academic experience both in the classroom and the laboratory. Specific activities are aimed at enhancing the university experience for student Veterans of the U.S. Armed Forces at WVU interested in pursuing Science, Technology, Engineering, and Math (STEM) careers. Carbon dioxide (CO2) is an attractive renewable resource for the production of chemicals; however, it is traditionally undervalued by the chemical industry because of its stability. Nevertheless, its broader utilization as a C1 feedstock could help shepherd a more sustainable carbon economy in the future. Catalytic olefin reductive carboxylation with CO2 is a potentially powerful way to create new carbon-carbon bonds while generating minimal waste. Professor Popp is focusing on two underdeveloped olefin reductive functionalization strategies: hetero(element)carboxylation and transfer hydrometallation/carboxylation. The former strategy employs element-boron reagents (where "element" includes boron, silicon, and tin) and copper catalysts to enable olefin difunctionalization using CO2 under mild conditions. Building upon insights gained from extensive kinetic study of iron-catalyzed hydromagnesiation, the latter strategy investigates new systems that achieve hydrozincation/carboxylation in a single catalytic reaction. Rational method optimization is accomplished in parallel with studies of catalytic reaction mechanisms using a combination of operando spectroscopic techniques, studies of stoichiometric reactions and preparation of plausible intermediates, as well as computational methods. In support of the broader impacts of the project, Professor Popp is organizing new training and career mentorship opportunities for STEM-interested student Veterans of the U.S. Armed Forces at WVU, collaborating with a primarily undergraduate institution in the Appalachian region on catalysis research relevant to this project, and developing a new multimedia tool for organic chemistry education. 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.