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Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N ‐Heterocycles and Reaction Mechanism Insights
Author(s) -
Pfeifer Viktor,
Certiat Marie,
Bouzouita Donia,
Palazzolo Alberto,
GarciaArgote Sébastien,
Marcon Elodie,
Buisson DavidAlexandre,
Lesot Philippe,
Maron Laurent,
Chaudret Bruno,
Tricard Simon,
Rosal Iker,
Poteau Romuald,
Feuillastre Sophie,
Pieters Grégory
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905651
Subject(s) - chemistry , catalysis , nanoclusters , ruthenium , molecule , nanomaterial based catalyst , combinatorial chemistry , hydrogen , deuterium , kinetic isotope effect , isotopic labeling , photochemistry , computational chemistry , organic chemistry , physics , quantum mechanics
Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D 2 or T 2 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 T 2 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.