Development of Catalytic Cyclization/Coupling Reactions for New Chemical Space

With the support of the Chemical Catalysis Program in the Division of Chemistry, Dr. Ramesh Giri of The Pennsylvania State University is developing catalysts that convert alkenes to cyclic molecules and then link them to another hydrocarbon fragment. In this work, close attention is paid to the use of earth-abundant transition metal catalysts, particularly those based upon Ni and Cu. This work is addressing the need for more efficient ways to make complex molecules that are critical to support the discovery of new pharmaceuticals and materials. The catalysts that Dr. Giri and his research team are studying are used to construct two carbon-carbon bonds in a single step to rapidly access value-added products and decrease the waste that accumulates from less efficient iterative processes. Selectivity elements are also being incorporated into catalyst design to control the fine structure of the complex molecules that can be generated using this technology. The ideas, concepts, and products of this work are being shared with local high schools through outreach activities to foster critical thinking in chemical science through the lens of sustainability.

Dr. Ramesh Giri and his research team are developing catalysts to advance cyclization/coupling strategies for alkene difunctionalization reactions. The three objectives of the program seek to tackle a combination of long-standing challenges and new directions in this area of reaction design. Beta-hydride elimination is a competing process in cyclization/coupling reactions that has significantly limited the scope of these transformations. The Giri group is designing new catalysts and catalyst-ligand combinations to avoid this classic fundamental challenge. To further broaden the scope of cyclization/coupling strategies towards accessing a broader range of complex molecules, this research program is also testing new enamine and silyl enol ether substrates, as well as exploring linearizable substrates with cleavable tethers. These activities are providing training opportunities for a diverse group of graduate and undergraduate students in catalysis, reaction design, and mechanistic study.

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.