CAREER: Synthesis Through Decarboxylative Metallation

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This research project addresses the development of catalytic decarboxylative metallation (conversion of a metal carboxylate to a metal alkyl through extrusion of carbon dioxide) as a method for accessing reactive transition metal reagents. Decarboxylative metallation is expected to provide an efficient strategy for the formation of synthetically-useful organometallic reagents directly from carboxylic acid derivatives. This project will explore the development of a variety of synthetically useful coupling reactions based on the concept of decarboxylative metallation, including decarboxylative alkylations, aminations, and selenylations. Decarboxylative alkene insertion reactions, wherein a metal catalyzes the replacement of the CO2 unit within an ester derivative by an electrophilic olefin, will also be explored. The factors (sterics, electronics, coordinating ability) that determine the rates of decarboxylative metallation will be determined. Peer-led discussion groups will be introduced in the classroom, facilitating the formation of learning relationships between diverse groups of students and enhancing conceptual understanding of chemistry. Graduate and undergraduate students will introduce children of the local community to chemistry through food-based experiments.With the support of this CAREER award from the Organic and Macromolecular Chemistry Program, Professor Jon A. Tunge, of the Department of Chemistry at the University of Kansas, is exploring new methods for the generation of reactive species under mild conditions and is developing new methods for the controlled synthesis of useful organic molecules. This research is expected to advance our fundamental knowledge of chemical reactions and will provide synthetic chemists with environmentally benign (green) methods for the synthesis of compounds that are important intermediates in the preparation of medicinally relevant natural products and small molecules. In addition, the proposed research will also provide a cornerstone for the training of undergraduate and graduate students. In the classroom, peer-led discussion groups will not only produce friendships between diverse groups of students but also enhance conceptual understanding of chemistry. In the interest of integrating research and education experiences, graduate and undergraduate students will introduce the children of the local community to chemistry through food-based experiments designed to stimulate and retain interest in chemistry.