CAREER: Bridging Synthesis and Computational Chemistry to Parameterize Noncovalent Interactions in Asymmetric Catalysis

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The Division of Chemistry Chemical Catalysis Program and the Established Program to Stimulate Competitive Research (EPSCoR) jointly support the research program of Professor Julie A. Pigza at the University of Southern Mississippi (USM). The Pigza research group is investigating new catalysts to transform petroleum and biomass feedstocks into important chemicals used in society. The improved catalysts meet the broader societal needs for important chemical building blocks while reducing environmental waste. The investigation is using computational methods to understand how the catalysts work to enable their improvement and usefulness. To accomplish these goals, graduate and undergraduate students are carrying out the synthetic, mechanistic, and computational aspects of this project. This is enriching interdisciplinary research training in the state of Mississippi. This research introduces two educational strategies to recruit and retain underrepresented groups into STEM research. The first is a Community College Bridge Program that is supporting STEM transfer student majors in their transition to USM through an authentic research experience, professional development workshops, and peer mentoring relationships. The second mechanism is a computational chemistry mini-course with a focus on catalysis utilizing an existing NSF-funded supercomputing facility at USM. The formation of carbon-carbon or carbon-heteroatom bonds with bifunctional hydrogen bond donor and acceptor organocatalysts has emerged as a viable alternative to transition metal catalysis. A key benefit to these organocatalysts is the exploitation of the innate reactivity of existing functional groups. This research investigates the ensemble of noncovalent interactions between a catalyst and substrate by combining chemical synthesis and computational quantum chemistry. The goal of this research is a deeper fundamental understanding of small molecule catalophore design mimicking those found in biological systems. Specifically, the systematic investigation of aromatic pi-pi stabilizing interactions between the catalyst and substrate is pursued using density functional theory to parameterize and rank the importance of these subtle non-covalent interactions. The specific aims probe underexplored bond transformations such as: (i) a transition metal-free asymmetric allylic alkylation, (ii) the generation of chiral, acyclic ethers, and (iii) the formation of ambiphilic methine nucleophiles and their addition to pi-bonds. The integrated educational and research components serve to train a diverse STEM workforce of high school, undergraduate, and graduate students within the Gulf South region with a focus on those students traditionally not exposed to research including community college students. This work also takes advantage of an existing NSF-funded supercomputing facility within the University.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.