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6 results on '"Del rosal, Iker"'

1. Hydrogen Isotope Exchange Catalyzed by Ru Nanocatalysts: Labelling of Complex Molecules Containing N-Heterocycles and Reaction Mechanism Insights.

Author

Pfeifer V, Certiat M, Bouzouita D, Palazzolo A, Garcia-Argote S, Marcon E, Buisson DA, Lesot P, Maron L, Chaudret B, Tricard S, Del Rosal I, Poteau R, Feuillastre S, and Pieters G

Subjects
Catalysis, Deuterium chemistry, Heterocyclic Compounds chemistry, Hydrogen chemistry, Imidazoles chemistry, Ruthenium chemistry
Abstract

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., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Published
2020
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2. Hydrogen isotope exchange catalyzed by Ru nanocatalysts: labelling of complex molecules containing N-heterocycles and reaction mechanism insights

Author

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, Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Optoélectronique Quantique (LPCNO), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), HPCs CALcul en MIdiPyrénées (CALMIP-OLYMPE, grant P1415), The Grand Equipement National de Calcul Intensif (GENCI-TGCC, grant 6211), European Project: 675071,H2020,H2020-MSCA-ITN-2015,ISOTOPICS(2016), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay, Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Modélisation Physique et Chimique (LPCNO), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), We acknowledge HPCs CALcul en MIdiPyrénées (CALMIP-OLYMPE, grant P1415) and the Grand Equipement National de Calcul Intensif (GENCI-TGCC, grant 6211) for generous allocations of computer time., Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Heterogeneous catalysis, Full Paper, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Imidazoles, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Full Papers, nanocatalysis, Deuterium, Tritium, Catalysis, Ruthenium, Heterocyclic Compounds, Deuteration, [CHIM]Chemical Sciences, N-heterocyclic carbenes, C−H Activation, hydrogen isotopic exchange, Isotopic exchange, C-H activation, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Hydrogen
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., 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.

Published
2020

3. Enantiospecific CH Activation Using Ruthenium Nanocatalysts.

Author

Taglang, Céline, Martínez‐Prieto, Luis Miguel, del Rosal, Iker, Maron, Laurent, Poteau, Romuald, Philippot, Karine, Chaudret, Bruno, Perato, Serge, Sam Lone, Anaïs, Puente, Céline, Dugave, Christophe, Rousseau, Bernard, and Pieters, Grégory

Subjects
RUTHENIUM, ENANTIOSELECTIVE catalysis, DEUTERIUM, HETEROCHAIN polymers, NANOPARTICLES
Abstract

The activation of CH bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific CH activation has been developed to date. We herein report an enantiospecific CH activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α-position of the directing heteroatom results from a four-membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles. [ABSTRACT FROM AUTHOR]

Published
2015
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4. Cover Picture: Enantiospecific CH Activation Using Ruthenium Nanocatalysts (Angew. Chem. Int. Ed. 36/2015).

Author

Taglang, Céline, Martínez‐Prieto, Luis Miguel, del Rosal, Iker, Maron, Laurent, Poteau, Romuald, Philippot, Karine, Chaudret, Bruno, Perato, Serge, Sam Lone, Anaïs, Puente, Céline, Dugave, Christophe, Rousseau, Bernard, and Pieters, Grégory

Subjects
RUTHENIUM, CATALYSIS, CHEMICALS
Abstract

Enantiospecific CH activation catalyzed by a ruthenium nanocatalyst enables the one‐step deuterium labeling of 25 bioactive compounds, such as amino acids and peptides, with full retention of configuration. In their Communication on page 10474 ff., G. Pieters et al. show that a four‐membered dimetallacycle is a key intermediate and suggest that the collective motion of surface species can facilitate the CH activation step by modulating the local electronic structure. [ABSTRACT FROM AUTHOR]

Published
2015
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5. Titelbild: Enantiospecific CH Activation Using Ruthenium Nanocatalysts (Angew. Chem. 36/2015).

Author

Taglang, Céline, Martínez ‐ Prieto, Luis Miguel, del Rosal, Iker, Maron, Laurent, Poteau, Romuald, Philippot, Karine, Chaudret, Bruno, Perato, Serge, Sam Lone, Anaïs, Puente, Céline, Dugave, Christophe, Rousseau, Bernard, and Pieters, Grégory

Subjects
CHEMISTRY periodicals, CHEMISTRY associations
Abstract

Die enantiospezifische C ‐ H ‐ Aktivierung mit einem Ruthenium ‐ Nanokatalysator ermöglicht die Deuterium ‐ Markierung von 25 bioaktiven Verbindungen, wie Aminosäuren und Peptiden, mit vollständigem Konfigurationserhalt. In der Zuschrift auf S. 10620 ff. schlagen G. Pieters et al. einen viergliedrigen Dimetallacyclus als Schlüsselintermediat vor und postulieren, dass die kollektive Bewegung von Oberflächenmolekülen die C ‐ H ‐ Aktivierung erleichtert, indem die lokale elektronische Struktur moduliert wird. [ABSTRACT FROM AUTHOR]

Published
2015
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6. Hydrido-Ruthenium Cluster Complexes as Models for Reactive Surface Hydrogen Species of Ruthenium Nanoparticles. Solid-State 2H NMR and Quantum Chemical Calculations.

Author

Gutmann, Torsten, Walaszek, Bernadeta, Xu Yeping, Wächtler, Maria, del Rosal, Iker, Grunberg, Anna, Poteau, Romuald, Axet, Rosa, Lavigne, Guy, Chaudret, Bruno, Limbach, Hans-Heinrich, and Buntkowsky, Gerd

Subjects
*RUTHENIUM, *DEUTERIUM, *SOLID-phase biochemistry, *ADDITION polymerization, *NUCLEAR magnetic resonance, *QUANTUM chemistry, *NANOPARTICLES
Abstract

The 2H quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state ²H MAS NMR techniques are used in the investigations of two ruthenium clusters, D4Ru4(CO)12 (1) and D2Ru6(CO)18 (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line- shape analysis of the ²H MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 ± 1 kHz, an asymmetry parameter of 0.67 ± 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu6(CO)18] (2-) and cationic [D3Ru6(CO)18]+ (2+). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2-, it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2+, the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the ²H nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles. [ABSTRACT FROM AUTHOR]

Published
2010
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