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

Alberto Palazzolo (1) , Timothée Naret (1) , Marion Daniel‐bertrand (1) , David‐alexandre Buisson (1) , Simon Tricard (2) , Bruno Chaudret (2) , Philippe Lesot (3) , Yannick Coppel (4) , Sophie Feuillastre (1) , Grégory Pieters (1)

1 SCBM - Service de Chimie Bio-Organique et de Marquage
2 LPCNO - Laboratoire de physique et chimie des nano-objets
3 CNRS - Centre National de la Recherche Scientifique
4 LCC - Laboratoire de chimie de coordination

Heterogeneous CatalysisTuning the Reactivity of a Heterogeneous Catalyst usingN-Heterocyclic Carbene Ligands for CH Activation ReactionsAlberto Palazzolo, TimothØe Naret, Marion Daniel-Bertrand, David-Alexandre Buisson,Simon Tricard, Philippe Lesot, Yannick Coppel, Bruno Chaudret, Sophie Feuillastre, andGrØgory Pieters*Abstract:We report the dramatic impact of the addition of N-heterocyclic carbenes (NHCs) on the reactivity and selectivityof heterogeneous Ru catalysts in the context of CH activationreactions. Using a simple and robust method, we prepareda series of new air-stable catalysts starting from commerciallyavailable Ru on carbon (Ru/C) and differently substitutedNHCs. Associated with CH deuteration processes, dependingon Ru/C-NHC ratios, the chemical outcome can be controlledto a large extent. Indeed, tuning the reactivity of the Ru catalystwith NHC enabled: 1) increased chemoselectivity and theregioselectivity for the deuteration of alcohols in organicmedia; 2) the synthesis of fragile pharmaceutically relevantdeuterated heterocycles (azine, purine) that are otherwisecompletely reduced using unmodified commercial catalysts;3) the discovery of a novel reactivity for such heterogeneous Rucatalysts, namely the selective C-1 deuteration of aldehydes

Mots clés: C-H activation; deuteration; heterogeneous catalysis; isotopic exchange; N-heterocyclic carbenes

Domaines: Chimie organique

Alberto Palazzolo, Timothée Naret, Marion Daniel‐bertrand, David‐alexandre Buisson, Simon Tricard, et al.. Tuning the Reactivity of a Heterogeneous Catalyst using N‐Heterocyclic Carbene Ligands for C−H Activation Reactions. Angewandte Chemie International Edition, 2020, 59 (47), pp.20879-20884. ⟨10.1002/anie.202009258⟩. ⟨hal-03001484⟩