Intramolecular Anodic Olefin Coupling Reactions

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With this award Professor Moeller will continue his work on the use of intramolecular anodic olefin coupling reactions in synthetic organic electrochemistry. This work involves the development of stereocontrolled synthetic methods based on radical cation chemistry and then the utilization of these chemical reactions in the synthesis of natural products. Proposed new method development on asymmetric electrochemical cyclizations utilizing chiral ketene acetals as substrates could lead to a new enantioselective carbon-carbon bond forming reaction. Reactions discovered with prior NSF support will be applied to several total syntheses in the new support period. The first two total syntheses involve key tandem cyclizations, the first of which are initiated by electrochemically generated enol ether radical cations, whereas the last two syntheses utilize highly functionalized furans as the initiating group. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Kevin D. Moeller of the Department of Chemistry at Washington University in St. Louis. Dr. Moeller will work on the use of electrolysis to generate chemical species which react with predictable patterns and selectivities. Use of electrolysis to generate reactive intermediates may prove to be a new "green" synthetic method with potential industrial applications. If large quantities of oxidants and reductants currently used in organic synthesis could be replaced by reliable electrochemical methods then many redox synthetic methods could be made more environmentally friendly. This group will also explore stereoselective oxidative cyclization reactions. These reactions produce molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer). Development of this family of reactions is one of the most important problems facing the pharmaceutical industry today. When developed, Dr. Moeller's work could be applied to the environmentally friendly syntheses of a number of biologically active molecules. Students trained during the course of this work will gain skills needed by the pharmaceutical industry which now produces a number of single enantiomer compounds.