Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N-Heterocycles and Reaction Mechanism Insights |
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Authors: | Dr Viktor Pfeifer Marie Certiat Dr Donia Bouzouita Dr Alberto Palazzolo Sébastien Garcia-Argote Elodie Marcon David-Alexandre Buisson Dr Philippe Lesot Prof Laurent Maron Dr Bruno Chaudret Dr Simon Tricard Dr Iker del Rosal Prof Romuald Poteau Dr Sophie Feuillastre Dr Grégory Pieters |
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Institution: | 1. SCBM, JOLIOT Institute, CEA, Université Paris-Saclay, 91191 Gif-sur-Yvette, France;2. LPCNO, Laboratoire de Physique et Chimie de Nano-Objets, UMR 5215 INSA-CNRS-UPS, Institut National des Sciences Appliquées, 135, Avenue de Rangueil, 31077 Toulouse, France;3. RMN en Milieu Orienté, ICMMO, UMR CNRS 8182, UFR d'Orsay, Université Paris-Saclay, Bât. 410, 91405 Orsay cedex, France |
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Abstract: | Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D2 or T2 gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC-MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T2 gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT-based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters. |
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Keywords: | C−H activation deuterium hydrogen isotopic exchange nanocatalysis tritium |
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