Harnessing Electroactive Bacteria for Microbial Redox Catalysis

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Abstract Biological catalysts are powerful tools for the synthesis of therapeutic materials and small molecules. Nevertheless, they are typically limited to native metabolic transformations conducted by well-defined enzymes. We hypothesize that the reaction space amenable to microbial catalysis can be extended by coupling respiratory electron flux from electroactive bacteria to redox-active transition metal catalysts in a process we term microbial redox catalysis (MRC). To address our hypothesis and highlight the advantages of MRC, we will use the model electroactive bacterium Shewanella oneidensis to control several reactions relevant to the medical industry. First, we will expand and optimize MRC living radical polymerization for a variety of monomers and metal catalysts. Next, we will use MRC to affect the dehalogenation of important pharmaceutical precursors. Finally, we will leverage MRC to enhance Palladium-catalyzed cross-coupling reactions. Overall, our program will combine the mechanism-driven design of synthetic catalysts with the tunability of microbial catalysts to provide new synthetic routes for a variety of health- relevant materials and molecules.