Intramolecular Anodic Olefin Coupling Reactions

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In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Kevin Moeller of the Department of Chemistry at Washington University in St. Louis will explore the chemistry of highly reactive radical cation intermediates and the molecular transformations that they trigger. The radical cation intermediates are generated electrochemically, a versatile technique that allows for structure-reactivity studies to be conducted on the radical cations. These studies serve to increase our mechanistic insight into the factors that control radical cation initiated reactions, and in so doing open up the opportunity to discover new synthetic methods for the construction of complex organic molecules. Since the electrochemical methods being developed can be conducted with the use of sunlight as the source of electricity, the chemistry holds great potential as a sustainable method. For example, chemical oxidation reactions utilize stoichiometric amounts of a chemical oxidant and in so doing require the formation of a stoichiometric reduction product as waste. In contrast, electrochemical oxidation reactions do not employ a chemical oxidant. Instead, the oxidation occurs by the loss of an electron to an anode surface. The required reduction reaction is channeled toward the formation of hydrogen gas at the cathode. Hence, a solar-driven electrochemical oxidation consumes only sunlight and generates hydrogen as the only byproduct. The proposed research will seek to expand this approach as a general synthetic method. Finally, this project will provide an excellent training environment for students, from pre-undergraduate to graduate, including those from historically underrepresented in the sciences.