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 is exploring the utility of electrochemistry as a tool for building the complex molecules that are frequently of interest to the pharmaceutical and chemical industries. The program has two main goals. The first is to gain a better understanding of the highly reactive intermediates central to synthetic reactions that increase the functionality of organic molecules. The second is to build the chemical insight necessary for the larger synthetic chemistry community to take full advantage of electrochemical methods. The broader impacts of the work are both scientific and educational. On the science front, the proposed electrochemistry holds great potential 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 no waste product. Such processes are both atom and energy economical. Because of these advantages, electrochemical methods are gaining in popularity, and numerous scientists from around the world enlist Professor Moeller to aide their own efforts to capitalize on the reactions. On the education front, the project supports 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 and science center educational programs to teach science to the general public. The science being pursued in this project capitalizes on mechanistic studies to both guide the development of new radical cation triggered cyclizations and illustrate how electrochemical methods can be used as synthetic tools. For example, recent observations that the removal of a second electron from a molecule plays a critical role in a successful cyclization reaction are being used to design new reactions that utilize this second oxidation step to both drive the processes to completion and to afford unique modes of reactivity. At the same time, new competition studies are being used to both probe the generality of these mechanistic findings, as well as to design new approaches to the synthesis of spirocyclic rings. New paired electrochemical methods, that take advantage of the reactions occurring at both electrodes in an electrochemical reaction, are being developed in order to maximize the energy economy of the processes. Each of these methods serves to illustrate, for the larger synthetic community, just how powerful electrochemical methods can be. As more synthetic chemists become interested in electrochemical reactions of their own design, the Moeller group remains poised to assist their efforts to implement them.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.