Chemoselective H/D exchange catalyzed by nickel nanoparticles stabilized by N-heterocyclic carbene ligands
Donia Bouzouita, Juan M. Asensio, V. F. Pfeifer, Alberto Palazzolo, Pierre Lecante, Grégory Pieters, Sophie Feuillastre, Simon Tricard, Bruno Chaudret
Abstract
With this work, we report the synthesis and full characterization of nickel nanoparticles (NPs) stabilized by N-heterocyclic carbene (NHC) ligands, namely 1,3-bis(cyclohexyl)-1,3-dihydro-2H-imidazol-2-ylidene (ICy) and 1,3-bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IMes). Although the resulting NPs have the same size, they display different magnetic properties and different reactivities, which result from ligand effects. In the context of H/D exchange on pharmaceutically relevant heterocycles, Ni@NHC shows a high chemoselectivity, avoiding the formation of undesired reduced side-products and enabling a variety of H/D exchange on nitrogen-containing aromatic compounds. Using 2-phenylpyridine as a model substrate, it was observed that deuteration occurred preferably at the α position of the nitrogen atom, which is the most accessible position for the C-H activation. In addition, Ni@IMes NPs are also able to fully deuterate the ortho positions of the phenyl substituents.