Pushing the Limits of Reactivity Principles for Organic Reactions

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In this project, funded by the Chemical Structure, Dynamics & Mechanisms B (CSDM-B) Program of the Chemistry Division, Professor 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 reactions of organic molecules. The goal of this research is to provide fundamental understanding of factors that control reactivity at a level useful for predicting laboratory reaction outcomes. 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 reactions to circumvent orbital symmetry constraints, access unusual reactivity of excited states and utilize entropy to control selectivity. In addition to the fundamental importance of the mechanistic models uncovered through this research, the project will serve to train students (graduate and undergraduate, several from underrepresented groups) in multidisciplinary approaches to mechanistic chemistry and expose them to diverse careers that employ such techniques. In addition, educational resources for teaching students about molecular vibrations during reactions, and methods for making applied computational chemistry accessible to blind and visually impaired students, will be developed and widely distributed. This research will focus on three classes of reactions, each with its own unique challenges: apparently forbidden pericyclic reactions, photochemical organic reactions displaying behavior akin to that of reactions with ground state post-transition state bifurcations, and organic reactions with entropy-controlled selectivity. Non-statistical dynamic effects will be analyzed and predicted for each, and general models of reactivity and selectivity will be constructed and used to design new reactions.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.