Fast and Selective β-C–H Borylation of N-Heterocycles with a Supramolecular Iridium Catalyst: Circumventing Deactivation Pathways and Mechanistic Insights - Université de Rennes Accéder directement au contenu
Article Dans Une Revue ACS Catalysis Année : 2023

Fast and Selective β-C–H Borylation of N-Heterocycles with a Supramolecular Iridium Catalyst: Circumventing Deactivation Pathways and Mechanistic Insights

Résumé

Selective iridium-catalyzed C-H bond borylations of unbiased or directing-group-free substrates typically occur under long reaction times and mild temperatures in order to avoid unselective processes including catalyst deactivation. Herein, we describe a supramolecular approach that enables the C-H bond borylation of challenging pyiridines and imidazoles in very short reaction times (up to 2 hours) with a negligible incubation period for catalyst activation. The catalyst is based on a highly rigid zinc-porphyrin substrate-recognition site in the secondary coordination sphere and a triazolopyridine chelating fragment attached to the first coordination sphere at iridium. The borylation occurs at the C-H bond from the substrate located at four chemical bonds apart from the molecular recognition site with the selectivity being exclusively imposed by the distance between the active site and the molecular recognition site regardless of the nature of the N,N-chelating fragment coordinating to iridium as further supported by DFT calculations. Additional studies (control experiments, NMR, SCXRD) unraveled key catalyst deactivation pathways in which up to three different partners (water, methoxide ligands from the iridium precursor and the triazolopyridine fragment) compete with the N-heterocycle substrate for binding to the molecular recognition site of the supramolecular catalyst. This fundamental understanding made possible the identification of a supramolecular catalyst featuring a 4-methyl substitution pattern in the first coordination sphere at iridium that provides a suitable balance of steric and electronic effects in both primary and secondary coordination spheres, thereby bypassing the manifold catalyst deactivation pathways. DFT calculations further indicated the importance of non-covalent interactions beyond the molecular recognition site on the stabilization of the different intermediates and transition sates.

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Chimie
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Dates et versions

hal-04106421 , version 1 (25-05-2023)

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Jonathan Trouvé, Purushothaman Rajeshwaran, Michele Tomasini, Antoine Perennes, Thierry Roisnel, et al.. Fast and Selective β-C–H Borylation of N-Heterocycles with a Supramolecular Iridium Catalyst: Circumventing Deactivation Pathways and Mechanistic Insights. ACS Catalysis, 2023, 13, pp.7715-7729. ⟨10.1021/acscatal.3c01742⟩. ⟨hal-04106421⟩
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