EXPLORATION OF THE ELECTRONIC STRUCTURES OF NITROGEN-RADICAL PRECURSORS FOR USE IN AMINATION
Susana Calderon, Erik Menke, Ryan Baxter, Hrant Hratchian.
University of California, Merced, Merced, CA.
Selective amination refers to the introduction of amine groups into organic systems, which is a highly versatile yet challenging synthetic practice common in pharmaceutical synthesis. As such, it is important to find new economical and efficient methods for amination. Synthetic approaches based on nitrogen-radical chemistry is a route our team is currently pursuing to address this critical challenge. To make significant progress requires an understanding of how and where nitrogen-radical precursors will be generated by nitrogen-oxygen-bond cleavage. This presentation focuses on our recent development of a protocol for predicting nitrogen-oxygen cleavage using computational chemistry. More specifically, this approach takes into account electronic and geometric changes the precursors undergo when neutral species are reduced to form radical anions. Using the B3LYP method with a 6-311+G(d) basis set, optimal structures of neutral compounds and corresponding anion states are determined and molecular orbitals are visualized to establish the presence or absence of antibonding character in the anion compounds. Our results indicate that our current computational protocol successfully predicts bond cleavage patterns and is being used to guide synthetic chemistry.