CAREER: Tautomeric-Ligand-Enabled Olefin Functionalization and Cross-Coupling Using Terrestrially Abundant Transition Metal Catalysts

University Of Rochester, Rochester NY

Investigators

Abstract

With the support of the Chemical Catalysis and Chemical Mechanism, Function, and Properties Programs in the Division of Chemistry, Professor C. Rose Kennedy of the University of Rochester is studying the development of new ligands that work in cooperation with earth-abundant metals to catalyze organic reactions. Typically, ligands are viewed as inert supports for the metal atoms that mediate the bond-forming and bond-breaking reactions used to make the ingredients of consumer goods, important agrochemicals, and medicines. By contrast, Professor Kennedy’s team is designing systems where tandem participation from the ligand enables chemical reactions that do not occur when using the metal alone. This approach is expanding the variety of molecules that can be produced efficiently from readily available starting materials, meeting a critical strategic need for sustainable manufacturing. Through parallel efforts in the classroom, Professor Kennedy is developing new assessment strategies for large-enrollment introductory organic chemistry classes. This approach is using metacognition and team-based learning to improve student retention and workforce preparation in STEM fields. A mini-summer course for high-school Upward Bound students is also being developed to improve access and inclusivity in STEM fields. Designing homogeneous catalysts that use ligand-enabled delivery of complex, multi-atomic reagents to transition metal centers is a powerful approach to expanding the toolbox of synthetic transformations promoted by earth-abundant first-row transition metals. Towards this goal, Professor Kennedy’s research team is developing a family of multifunctional pyridone ligands that, when used in combination with first-row transition elements such as nickel, shuttle complex reagents through the metal’s secondary coordination sphere. This approach is providing a new strategy for engaging poorly reactive but otherwise appealing transmetallating agents and electrophiles. To understand the synergy between the metal and pyridone ligand, the elementary steps relevant to olefin functionalization and cross coupling are being evaluated in detail using a combination of computational and experimental mechanistic tools. Resulting structure-reactivity-selectivity relationships are then being used to invent new catalytic reactions that combine readily available and user-friendly reagents to generate value-added, C(sp3)-rich building blocks for fine chemical synthesis. In the lab, this award is also supporting hands-on chemistry-research training for University of Rochester undergraduate and graduate students as well as Rochester-area high school and community college students. 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.