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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Bibliographic Details
Published in:Angewandte Chemie International Edition Vol. 59; no. 47; pp. 20879 - 20884
Main Authors: Palazzolo, Alberto, Naret, Timothée, Daniel‐Bertrand, Marion, Buisson, David‐Alexandre, Tricard, Simon, Lesot, Philippe, Coppel, Yannick, Chaudret, Bruno, Feuillastre, Sophie, Pieters, Grégory
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 16.11.2020
Wiley Subscription Services, Inc
Wiley-VCH Verlag
Edition:International ed. in English
Subjects:
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
Online Access:Get full text
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Summary: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.
Bibliography:Agence Nationale de la Recherche (ANR)
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202009258