Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N‐Heterocycles and Reaction Mechanism Insights. Issue 22 (9th March 2020)

• Record Type: Journal Article
• Authors: Pfeifer, Viktor; Certiat, Marie; Bouzouita, Donia; Palazzolo, Alberto; Garcia‐Argote, Sébastien; Marcon, Elodie; Buisson, David‐Alexandre; Lesot, Philippe; Maron, Laurent; Chaudret, Bruno; Tricard, Simon; del Rosal, Iker; Poteau, Romuald; Feuillastre, Sophie; Pieters, Grégory
• Is Part Of: Chemistry. Volume 26:Issue 22(2020)
• Page Start: 4988
• Page End: 4996
• Publication Date: 2020-03-09
• Subjects: C−H activation -- deuterium -- hydrogen isotopic exchange -- nanocatalysis -- tritium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201905651
• Languages: English
• ISSNs: 0947-6539

Abstract

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. 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. In terms of application, the high incorporation of deuterium atoms allows the synthesis of deuterated internal standards for LC/MS quantification and the efficacy of the catalytic process permits the preparation of complex radiolabelled drugs owning high specific activities by using a subatmospheric pressure of T2 gas.