Studies on Electrophilic Metal Complexes in Lewis Acid-Catalyzed C-C Bond-Forming Reactions

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In this collaborative project, the catalytic behavior of cationic octahedral iridium(III) complexes will be investigated in C-C bond-forming reactions. First, thorough investigation of the mechanism of Nazarov cyclization will be conducted, using Ir(III) complexes as a tool to study the complex sequence of steps involved in the reaction. Second, selective methods to conduct new tandem sequences and new methods for enol alkylation using Lewis acidic Ir(III) complexes will be developed. Finally, chiral catalysts for asymmetric Nazarov cyclizations and multi-step sequences based on cationic Ir(III) systems will be synthesized and studied, including new C2 symmetric complexes closely related to the known catalysts possessing adjacent labile binding sites on the catalyst metal center. With this award, the Organic and Macromolecular Chemistry Program is supporting the research collaboration of Professor Alison Frontier and Professor Richard Eisenberg of the Department of Chemistry at the University of Rochester. Research in the catalysis of electrophilic Ir(III) complexes aids in the development of new synthetic methodologies needed for the preparation of commodity and fine chemicals. Increasing molecular complexity through catalysis represents a key means of creating new useful compounds of potential impact beyond the research laboratory.