CAREER: Chemical Methods for Organic Synthesis Using Nucleophilic Allyl- and Alkylmetal Catalysts

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Proposal Abstract This project will address the development of catalyst-controlled asymmetric allylation and alkylation reactions. While many methods for enantioselective allylation and alkylation reactions exist, new methods are required for efficient and practical reactions of complex synthetic intermediates. A central hypothesis is that nucleophilic allylmetal and alkylmetal complexes will be formed in situ by transmetallation mechanisms and these species will undergo ligand-controlled reactions with electrophiles. Preliminary studies have uncovered a new class of nucleophilic allylpalladium complexes with bidentate neutral N-heterocyclic carbene ligands, which have been used to develop catalytic allylation reactions of N-acylpyrroles and alkylidene malononitriles. The development of stereoselective conjugate allylation reactions of broad scope with mild reaction conditions is planned. In addition, new mechanisms for alkylation reactions of electrophiles by generating alkylmetal complexes from boronic acids with first row transition metals will be proposed. Studies to elucidate the mechanisms of the transformation will also be performed. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Elizabeth Jarvo of the Department of Chemistry at the University of California, Irvine. Professor Jarvo's research efforts revolve around the development of selective methods for the formation of C-C bonds. Such chemistry will contribute to environmentally benign methods for chemical synthesis as the transformations will be practical and efficient, which will minimize the environmental cost of the transformation. Successful development of the methodology will have an impact on synthesis in the pharmaceutical and agricultural industries.