Intramolecular Anodic Olefin Coupling Reactions

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With this award, the Chemical Synthesis Program in the Division of Chemistry is funding Professor Kevin Moeller of the Department of Chemistry at Washington University in St. Louis to use electrochemical methods to probe the highly reactive intermediates central to synthetic reactions that increase the functionality of organic molecules. The effort serves to build a foundation for the design of new, more efficient synthetic routes to molecules of interest to the pharmaceutical and chemical industries and to develop electrochemistry as a sustainable tool for accomplishing those transformations. The broader impacts of the work are both scientific and educational. On the science front, this project illustrates for others the overall utility of electrochemistry as a sustainable technique. The reactions can be run in a manner that uses sunlight (or any other clean source of electricity) as the only source of energy and generates hydrogen gas as the only byproduct. For this reason, scientists from around the world enlist Professor Moeller to aid their own efforts to capitalize on electrochemical methods. On the education front, the project will support the training of young scientists in both chemical and electrochemical techniques, the development of undergraduate laboratory experiments that expose students to their first electrochemical reactions, and the continued implementation of outreach activities that utilize zoo educational programs to teach science to the general public. The specific science being pursued in this project capitalizes on a combination of competition studies and cyclic voltammetry to probe the mechanistic underpinnings of new radical cation-triggered cyclizations. The mechanistic insight is used to develop new synthetic methods that demonstrate how to best take advantage of the reactions. Both the mechanistic and synthetic studies benefit greatly from the use of electrochemistry. Electrochemical methods allow for generation of the reactive radical cations from a wide variety of substrates with nearly identical reaction conditions. This enables the Moeller group to make systematic changes to the structure of a radical cation and then probe how those changes alter the chemical reactivity of the intermediate. The same technique is employed to conduct scalable synthetic reactions, an effort that demonstrates the synthetic utility of electrochemistry and one that is expected to generate interest in electrochemical methods by others in the synthetic community.