Developing Catalytic Methods to Control Cationic Electrocyclizations

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Alison Frontier and Professor Richard Eisenberg of the Department of Chemistry at the University of Rochester will develop strategies to control reactivity and different types of selectivity in cationic electrocyclizations using catalytic methods. Specifically, they will attempt to achieve catalytic, asymmetric control of several classes of electrocyclization processes, including 1) aromatic/heteroaromatic Nazarov cyclization (substrates with relatively low reactivity), 2) a new version of the cationic Piancatelli cyclization (substrates with relatively high reactivity), and 3) a cyclization/ rearrangement sequence able to convert a planar substrate into a cyclopentenone product with adjacent quaternary centers. This third reaction sequence will be employed in a synthesis of enokipodin antibiotics.Increasing molecular complexity through catalysis represents a key means of creating new useful compounds of potential impact beyond the research laboratory. Furthermore, the research that students conduct on this project, from the undergraduate to the postdoctoral level, connects intimately with their education and professional training, and moves them effectively along the path to becoming independent scientists. Laboratory activities, detailed analyses and the formulation of new experiments form the foundation of a true collaboration between these two professors, who will serve as co-advisors for all project participants. These efforts will be complemented by other activities that benefit student researchers while building a community of scientists. In particular, addition of new scientific content to the Not Voodoo website will be prioritized, to disseminate the knowledge of experts to website visitors in more isolated laboratory environments. These innovative activities, stimulated by research and communication, enhance the attractiveness of chemistry and thus contribute in an essential way to the broader impacts of the science studied.