Novel Synthetic Methods

With the support of the Chemical Synthesis Program in the Division of Chemistry, Professor Vladimir Gevorgyan and his graduate and undergraduate students at the University of Texas at Dallas are developing mild, efficient, and selective reaction methodology for synthesizing organic molecules. In particular, the Gevorgyan group is developing organic chemistry methodology to convert readily available feedstock chemicals that have an abundance of Carbon–Hydrogen (C–H) bonds into other, more highly valued chemicals that contain new bonds that are more commonly found in medicines and materials (Carbon–Oxygen (C–O), Carbon–Nitrogen (C–N), Carbon–halogen (C–X), Carbon–Carbon (C–C), Carbon–Boron (C–B), etc.). To carry out these transformations, Professor Gevorgyan’s team is developing reaction methodology that is free of costly and potentially toxic and/or explosive reagents. In addition to providing new and effective routes to building complex molecules and materials of importance, the broader impacts of the proposed work include outreach activities that are aimed at recruiting undergraduate students, including underrepresented minority students, into research where their potential and career possibilities will be enhanced. In this project, the Gevorgyan team is developing new mild methods for the generation of carbon- and heteroatom-centered radicals and unlocking their reactivity. The approach under development relies on novel donor-acceptor (DA) complexes capable of the reduction of electrophilic intermediates using single electron transfer (SET). Their work is being carried out using visible light initiation leading to the generation of a precursor radical that undergoes atom transfer (AT) or hydrogen atom transfer (HAT) to generate transposed radicals. These new radicals can then engage in a number of diverse synthetic transformations, including C(sp3)−H bond functionalization reactions. The factors favoring the efficient formation of DA complexes, as well as SET, AT, and HAT processes, will be investigated under this award. It is believed that these methods, when fully developed, will not only deepen our understanding of electron-transfer chemistry, but they will also substantially broaden the tools that are available for the synthesis and late-stage modification of complex molecules and drugs. 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.