Modern Theoretical Carbocation Chemistry

University Of California-Davis, Davis CA

Investigators

Abstract

The Chemical Structure, Dynamics and Mechanism Program of the NSF Chemistry Division supports the research of Professor Dean Tantillo in the Department of Chemistry at The University of California-Davis. Professor Tantillo and his students are using modern computational chemistry methods to explore new principles governing chemical reactivity. The principles uncovered transform how organic chemists predict mechanisms and product distributions for many reactions that lead to complex molecules. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project is used to train students from diverse backgrounds in multidisciplinary approaches to mechanistic chemistry and expose them to careers that employ such techniques. In addition, new methods for making applied computational chemistry accessible to blind and visually impaired students are being developed as part of an effort to encourage this group to pursue careers in STEM fields. The results of this research are disseminated, in part, via an outreach program in partnership with a local arboretum. This research advances knowledge in mechanistic organic chemistry through the construction of detailed mechanistic models for carbocation reactivity. In particular, unusual potential energy surfaces for carbocation rearrangements are characterized, non-statistical dynamic effects on carbocation behavior are analyzed and predicted, and models of reactivity are pushed through to the design and testing of new reactions. The specific goals of this project are: (1) To elucidate general principles for controlling the dynamical behavior of species involved in concerted reactions with multiple asynchronous events (2) To design a reaction with a post-transition state bifurcation and predict its product distribution ahead of laboratory experiments. (3) To develop the theozyme dynamics approach into a tool for understanding and designing catalysts that make use of relatively weak noncovalent interactions.