Chemistry Commons^™

Dft-Assisted Design And Evaluation Of Bifunctional Copper(I) Catalysts For The Direct Intermolecular Addition Of Aldehydes And Ketones To Alkynes, Jacob D. Porter, Eric Greve, Abdulmohsen Alsafran, Adam R. Benoit, Sergey V. Lindeman, Chris Dockendorff

Chemistry Faculty Research and Publications

Bifunctional catalysts containing discrete metal pi-acid and amine sites were designed and investigated for the direct intermolecular addition of aldehydes and ketones to unactivated alkynes. Copper(I)-based catalysts were prioritized based on intramolecular (Conia-ene type) reactions, and complexes were designed with tridentate ligands and potentially hemilabile heterocyclic spacers. The structures of the designed catalysts were computed using density functional theory (DFT), and the relative energies of putative catalytic intermediates were estimated and used to prioritize catalyst designs. Novel bifunctional precatalysts containing a thiazole spacer were synthesized via a 9-step sequence and combined with transition metals before screening for the direct addition …