New Asymmetric Anionic Reaction Cascades

With the support of the Chemical Synthesis Program of the Division of Chemistry, Professor Jon Njardarson of the University of Arizona is developing new chemical reaction cascades in that leverage readily available feedstock materials in concert with negatively charged reaction partners to trigger sequences of reactions that produce higher-value fine chemical products. These new reaction processes will have broader scientific impacts by enabling researchers in industry and academia to construct and manufacture target architectures more efficiently, and the fundamental studies of reaction mechanisms will support the design of other new reactions. Broader impacts of this project also include workforce development and the continued dissemination of publicly available and popular educational work products from the PI and team. This project is focused on making significant advances on the asymmetric dienolate cascade reaction platform that the PI’s lab has been developing. Specific advances include in situ trapping of lithium enamides at carbon or nitrogen to expand the type of products that can be assembled in one pot, and realizing the formation of products containing all carbon quaternary centers. Detailed mechanistic investigations have opened and will continue to open new directions of reaction development, including the proposed routes to chiral lactams and atropisomers. This project is also focused on efficient assembly of chiral complex aromatic nitrogen heterocycles and fused ring structures via pericyclic and radical-metal-mediated cascades respectively, with the goal of increasing the impact of the chiral auxiliary. The suite of reactions being developed is expected to impact chemical synthesis and its applications in medicine, materials, and other areas. 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.