Organic Free Radical Chemistry

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The focus of this research is to develop a systematic study of radical heterolysis reactions. The research will include kinetic and mechanistic studies of radical cations, focusing on radical cations believed to be involved in the rearrangement of methylmalonyl/coenzyme-A to succinate in vivo. Strained 3-membered ring "reporter groups" will be synthesized and opened photolytically to measure the rate of radical formation by UV spectroscopy. This approach is well suited for the study of alpha- and beta-carboxylate functionalized radicals believed to be involved in the chemistry of B12 dependent enzymes. With this Renewal award, the Organic and Macromolecular Chemistry Program is supporting the research and educational efforts of Dr. Martin E. Newcomb of the Department of Chemistry at the University of Illinois, Chicago. Professor Newcomb will focus his research on the use of lasers to break critical bonds related to the function of vitamin B12 in the human body. This work will have impact on the design of new methods for catalysis in the pharmaceutical industry, as well as important impacts on the understanding of enzyme function. The educational activity of the award revolves around the training of graduate students in the study of short-lived chemical intermediates.