Modulating Kinetic Reactivity of Organic Molecules - A Focus on Dynamic Control

In this project, funded by the Chemical Mechanism, Function, and Properties Program of the Chemistry Division, Professor Dean Tantillo of the Department of Chemistry at the University of California, Davis is using modern computational chemistry methods to explore the limits of reactivity principles for organic reactions of fundamental and synthetic interest. The overall goal is to provide fundamental understanding of factors that control reactivity, including non-statistical dynamic effects, at a level useful for predicting laboratory reaction outcomes. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project will be used to train students in multidisciplinary approaches to mechanistic chemistry and expose them to careers that employ such techniques. Educational resources will be developed and widely distributed. This research will advance knowledge in mechanistic organic chemistry through the construction of new mechanistic models, including those based on non-statistical dynamic effects that allow for the control of selectivity in the face of post-transition state bifurcations, and those that predict the feasibility of both dyotropic reactions with transition metal-based migrating groups and homopericyclic reactions. The principles uncovered will likely transform how organic chemists predict mechanisms and product selectivity for reactions of structurally complex organic and organometallic molecules. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.