Wen, Y.Fernández-Sabaté, M.Lledós, Agustí (Lledós i Falcó)Sciortino, GiuseppeEills, JamesMarco Rius, IreneRiera i Escalé, AntoniVerdaguer i Espaulella, Xavier2024-10-092024-10-092024-04-191433-7851https://hdl.handle.net/2445/215646A combined computational and experimental approach allowed us to develop overall the most selective catalyst for the direct hydrogenation of N-methyl, N-alkyl and N-aryl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99 % enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H-bonding of the imide C=O with the substrate iminium ion and a stabilizing π–π interaction with the cyclometallated ligand. The cyclometallated ligand thus exhibits a unique mode of action, serving as a template for the H-bond directed approach of the substrate which results in enhanced selectivity. The catalyst (2) has been synthesized and isolated as a crystalline air-stable solid. X-ray analysis of 2 confirmed the structure of the catalyst and the correct position of the imide C=O groups to engage in an H-bond with the substrate. 19F NMR real-time monitoring showed the hydrogenation of N-methyl imines catalyzed by 2 is very fast, with a TOF of approx. 3500 h−1.1 p.application/pdfengcc-by (c) Wen, Y., et al, 2024http://creativecommons.org/licenses/by/3.0/es/HidrogenacióIridiHydrogenationIridiuminfo:eu-repo/semantics/article7486312024-10-09info:eu-repo/semantics/openAccess