Tuning the Reactivity of a Heterogeneous Catalyst using N‐Heterocyclic Carbene Ligands for C−H Activation Reactions

We report the dramatic impact of the addition of N‐heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C−H activation reactions. Using a simple and robust method, we prepared a series of new air‐stable catalysts starting from commercially av...

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Vydané v:	Angewandte Chemie International Edition Ročník 59; číslo 47; s. 20879 - 20884
Hlavní autori:	Palazzolo, Alberto, Naret, Timothée, Daniel‐Bertrand, Marion, Buisson, David‐Alexandre, Tricard, Simon, Lesot, Philippe, Coppel, Yannick, Chaudret, Bruno, Feuillastre, Sophie, Pieters, Grégory
Médium:	Journal Article
Jazyk:	English
Vydavateľské údaje:	WEINHEIM Wiley 16.11.2020 Wiley Subscription Services, Inc Wiley-VCH Verlag
Vydanie:	International ed. in English
Predmet:	Alcohols Aldehydes Carbenes Catalysts Chemical Sciences Chemistry Chemistry, Multidisciplinary C−H activation Deuteration heterogeneous catalysis isotopic exchange N-heterocyclic carbenes Organic chemistry Physical Sciences Reactivity Regioselectivity Science & Technology Selectivity Tuning SELECTIVE DEUTERATION deuteration isotopic exchange HYDROGENATION heterogeneous catalysis STABILIZATION BOND FUNCTIONALIZATION RU NANOPARTICLES SULFUR ALCOHOLS C-H activation REGIOSELECTIVE DEUTERATION N-heterocyclic carbenes
ISSN:	1433-7851, 1521-3773, 1521-3773
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Shrnutí:	We report the dramatic impact of the addition of N‐heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C−H activation reactions. Using a simple and robust method, we prepared a series of new air‐stable catalysts starting from commercially available Ru on carbon (Ru/C) and differently substituted NHCs. Associated with C−H deuteration processes, depending on Ru/C‐NHC ratios, the chemical outcome can be controlled to a large extent. Indeed, tuning the reactivity of the Ru catalyst with NHC enabled: 1) increased chemoselectivity and the regioselectivity for the deuteration of alcohols in organic media; 2) the synthesis of fragile pharmaceutically relevant deuterated heterocycles (azine, purine) that are otherwise completely reduced using unmodified commercial catalysts; 3) the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely the selective C‐1 deuteration of aldehydes. The addition of N‐heterocyclic carbenes on Ru/C induces a catalytic activity switch to favor hydrogen isotope exchange over reductive deuteration. This catalyst modification led to an increase in regio‐ and chemoselectivity in the context of the C−H deuteration of pharmaceutically relevant substructures, as well as to the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely selective C‐1 deuteration of aldehydes.
Bibliografia:	Agence Nationale de la Recherche (ANR) ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.202009258