SusChEM: Mechanistic Investigations of Oxidative Carbon-Hydrogen Functionalization Reactions

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The Chemical Synthesis Program of the Chemistry Division supports the project by Professor Brenton DeBoef of the University of Rhode Island. Professor DeBoef is developing new chemical reactions that convert carbon-hydrogen bonds to carbon-nitrogen or carbon-carbon bonds. These reactions are significant because most organic molecules are constructed with a skeletal framework containing carbon-carbon and carbon-nitrogen bonds, surrounded by many carbon-hydrogen bonds on their periphery. Consequently, the ability to directly convert selected carbon-hydrogen bonds to other bonds is a valuable tool for chemists. The key to the development of these new reactions is the use of new gold and iron-based catalysts. These new reactions will help chemists construct technologically relevant, complex molecules such as pharmaceuticals, conducting polymers and organic dyes. Additionally, Professor DeBoef has formed a joint research and training program with the Community College of Rhode Island in which students in the Chemical Technology program synthesize a potential Alzheimer's drug. This collaboration is having an impact by expanding research infrastructure and scientific workforce training. The overarching objective of the project is to systematically test mechanistic hypotheses concerning the catalytic synthesis of carbon-carbon (C-C) and carbon-nitrogen (C-N) bonds via oxidative carbon-hydrogen (C-H) bond activation. Accomplishing these goals provides fundamental knowledge about the mechanistic steps by which noble or earth-abundant transition metal catalysts cleave strong, non-acidic C-H bonds. Specifically, this proposal seeks to discover the active catalytic species in a gold catalyzed regioselective C-H amination reaction and an iron-catalyzed C-H arylation reaction. DeBoef has hypothesized that the former reaction is catalyzed by a unique dimeric gold species. An iron catalyst, whose resting state is in the unique +1 oxidation state, is hypothesized to catalyze the latter reaction. The fundamental knowledge gained by this work facilitates the development of novel chemical reactions and synthetic schemes. The DeBoef group contributes to the training of a diverse workforce in science by providing an excellent training environment for both graduate and undergraduate students, including women and minorities. Additionally, the outreach work with the Community College of Rhode Island provides aspiring chemical technicians with a meaningful and marketable research experience.