New Strategies for Investigating Oxidative Aliphatic Carbon-carbon Bond Cleavage Reactions

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In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Lisa M. Berreau of the Department of Chemistry at Utah State University (USU) investigates how anions and divalent metals influence chemical reactions leading to the oxidative cleavage of carbon-carbon bonds in molecules of relevance to catalysis and biological systems. Results of these studies may drive new approaches in the preparation of useful chemicals, including pharmaceuticals. These studies also provide insight into how an enzymatic system cleaves carbon-carbon bond, which helps to understand biological transformations. This project lies at the interface of inorganic, organic, and biological chemistry and is well suited for training students at all educational levels and with interests in many different areas of chemistry. Professor Berreau is the faculty advisor for the USU Chemistry Club, which is involved in numerous outreach activities involving K-12 students. Professor Berreau is also active in student career development activities and participates in recruiting activities directed at engaging students underrepresented in science. Specifically, synthetic and reactivity studies of metal enolate complexes are being used to elucidate how anions and divalent metals influence the reaction pathways of dioxygen-dependent aliphatic carbon-carbon bond cleavage reactions within the enolate moiety. Anion effects on dioxygen activation and oxygen-oxygen bond scission are being defined in Cu(II)/dioxygen reactions involving oxidative cleavage of a chlorodiketonate ligand. This reactivity is being explored as a function of the coordination properties of the supporting chelate ligand and the structure and electronic properties of the diketonate moiety. Metal ion effects on the dioxygen reactivity of divalent metal acireductone complexes are being investigated to reveal how acireductone dioxygenases control the regioselectivity of oxidative aliphatic carbon-carbon bond cleavage via the metal ion content of the enzyme.