Mechanisms of Complex Carbocation Rearrangements

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With this Renewal Award, the Chemical Structure, Dynamics, and Mechanisms Program continues to support Professor Dean J. Tantillo for a proposal that uses modern computational chemistry, coupled with laboratory experiments to uncover the fundamental principles of reactivity that govern mechanisms of carbocation rearrangements leading to terpene natural products. The goals of this research are to (a) use modern quantum chemical methods to assess the energetic viability of various complex carbocation cyclization mechanisms leading to terpene natural products and to characterize the electronic structures of the intermediates and transition state structures involved in these processes. And (b), assess the ability of these intermediates and transition state structures to engage in noncovalent/intermolecular interactions with functional groups present in enzyme active sites. In short, this project will uncover general principles of carbocation reactivity that are relevant to a wide variety of complex rearrangements. This award will lead to an increased understanding of unusual types of chemical bonding, support the training of postdoctoral, graduate and undergraduate students, and build a network of collaborations between experimentalists and computational chemists. In addition to the fundamental importance of the chemistry uncovered through this research, the projects pursued will be used to provide students with multidisciplinary approaches to mechanistic chemistry and expose them to careers that utilize such expertise. The results of this research will be incorporated into the University of California COSMOS Summer Program for high school students interested in science, and a biennial symposium that exposes postdoctoral, graduate, undergraduate, and high school students to careers in theoretical chemistry.