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25 results on '"Galiana‐Cameo, María"'

2. Iridium(i) complexes with bidentate NHC ligands as catalysts for dehydrogenative directed C-H silylation

Author

Centre National de la Recherche Scientifique (France), Agence Nationale de la Recherche (France), Ministère de l’Enseignement supérieur et de la Recherche (France), National Science and Technology Development Agency (Thailand), Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Manguin, Romane, Galiana-Cameo, María, Kittikool, Tanakorn, Barthes, Cécile, Thongpaen, Jompol, Bancal, Etienne, Mallet-Ladeira, Sonia, Yotphan, Sirilata, Castarlenas, Ricardo, Mauduit, Marc, Sortais, Jean-Baptiste, Baslé, Olivier, Centre National de la Recherche Scientifique (France), Agence Nationale de la Recherche (France), Ministère de l’Enseignement supérieur et de la Recherche (France), National Science and Technology Development Agency (Thailand), Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Manguin, Romane, Galiana-Cameo, María, Kittikool, Tanakorn, Barthes, Cécile, Thongpaen, Jompol, Bancal, Etienne, Mallet-Ladeira, Sonia, Yotphan, Sirilata, Castarlenas, Ricardo, Mauduit, Marc, Sortais, Jean-Baptiste, and Baslé, Olivier

Abstract

A series of (NHC)(cod)Ir(I) complexes bearing NHC-carboxylate ligands were efficiently synthesized and fully characterized. Their solid-state structures confirmed the bidentate coordination mode of these LX-type NHC ligands. These unprecedented iridium(I) complexes demonstrated efficient catalytic activities in dehydrogenative directed C–H silylation of arenes, and allowed for excellent ortho-selectivity control with aromatic silylating agents.

Published
2023

3. Iridium(i) complexes with bidentate NHC ligands as catalysts for dehydrogenative directed C–H silylation

Author

Manguin, Romane, primary, Galiana-Cameo, María, additional, Kittikool, Tanakorn, additional, Barthes, Cécile, additional, Thongpaen, Jompol, additional, Bancal, Etienne, additional, Mallet-Ladeira, Sonia, additional, Yotphan, Sirilata, additional, Castarlenas, Ricardo, additional, Mauduit, Marc, additional, Sortais, Jean-Baptiste, additional, and Baslé, Olivier, additional

Published
2023
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5. DFT studies on metal ligand cooperative on alkyne transformations catalyzed by Rh-NHC complexes

Author

Polo, Víctor, Urriolabeitia, Asier, Galiana-Cameo, María, Castarlenas, Ricardo, Polo, Víctor, Urriolabeitia, Asier, Galiana-Cameo, María, and Castarlenas, Ricardo

Abstract

In this work, the electronic and steric effects introduced by ligands on the Rh N-heterocyclic carbene (NHC) template are analyzed using DFT calculations. Inclusion of innocent ligands, such as chloride, or non-innocent ligands, such as pyridinato group, opens new mechanistic scenarios as proven experimentally. Then, different products may be obtained at mild conditions by catalyst design, in the first case, selective alkyne gem dimerization by proton transfer is achieved while inclusion of a chlrodine ligand to the metal, yields C-C and C-N bond couplings of the alkyne with the pyridonato group. The different roles of the metal and the ligands are unveiled calculating the DFT free energy profiles. The obtained profiles are in agreement with experimental KIE studies. In particular, it is remarkable that up to three ligands attached to the metal play key and complementary roles along the catalytic cycle. Hence, the NHC ligand favors the Rh(I) to Rh(III) oxidative addition and introduces steric repulsion avoiding isomerization reactions. The chloride ligand removes electron density of the Rh(III), favoring the formation of metallacycle over vinylidene intermediates. Finally, the hemilabile pyridonato ligand may play two roles, i) assistance to the C-H alkyne bond breaking by accepting the proton or ii) performing a nucleophilic attack towards nucleophilic carbon atom of the metallacycle intermediate.

Published
2022

6. Alchemical Design of Pharmacological Chaperones with Higher Affinity for Phenylalanine Hydroxylase

Author

Conde-Giménez, María, primary, Galano-Frutos, Juan José, additional, Galiana-Cameo, María, additional, Mahía, Alejandro, additional, Victor, Bruno L., additional, Salillas, Sandra, additional, Velázquez-Campoy, Adrián, additional, Brito, Rui M. M., additional, Gálvez, José Antonio, additional, Díaz-de-Villegas, María D., additional, and Sancho, Javier, additional

Published
2022
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7. RH─NHC complexes: a tool for the synthesis of alkenyl oxypyridines as potential biologically active intermediates

Author

Galiana-Cameo, María and Castarlenas, Ricardo

Abstract

Resumen del póster presentado a la XXXVIII Reunión Bienal de la Real Sociedad Española de Química, celebrada en el Palacio de Congresos de Granada, del 27 de junio al 30 de junio de 2022., The C–H activation and the alkyne hydrofunctionalization are reactions of great interest in the preparation of organic compounds with high added value. On the other hand, the 2-pyridone scaffold can be found embedded in many biologically relevant compounds, including some drugs approved by the FDA for the treatment of cancer, HIV or pulmonary fibrosis. Our research group has extensive experience in the design of Rh catalysts with N-heterocyclic carbene (NHC) ligands as selective Markovnikov-type catalysts in alkyne hydrofunctionalization. Due to the interest of these molecules, the proper choice of auxiliary ligands within the coordination sphere of the metal is essential to control the selectivity of the process and achieve good catalytic efficiency. In a previous work related to alkyne dimerization, it was observed that the 2-pyridonate ligand coordinated to the Rh-NHC scaffold behaves as a proton shuttle through a deprotonation-protonation mechanism. This catalytic system is also effective in the hydropyridonation of alkynes, specifically obtaining the gem isomer. In addition, the chemoselectivity of the process is directed towards the formation of the O-alkenylation product (Figure 1), thermodynamically less favored, due to the N-coordination of the 2-pyridone derivatives. Mechanistic studies in combination with DFT calculations support a hydride-free pathway. Conversely, the C–O coupling operates through a metallacyclopropene intermediate and the IPr carbene, with bulky groups in its structure, stabilizes it and favors its release from the metal center. Owing to the importance of this type of molecules as synthetic intermediates related to structures of biological interest, the design of new and more efficient catalysts offers promising results in this research area.

Published
2022

16. In vitro validation of new PAH binding compounds for non-kuvan responsive PKU patients

Author

Conde-Giménez, María, Salillas, Sandra, Galano-Frutos, Juan J., Mahía Moros, Alejandro, Galiana-Cameo, María, Díaz de Villegas, María D., and Sancho, Javier

Abstract

Resumen del trabajo presentado a la IX International Conference BIFI: New Challenges in Molecular Biotechnology, celebrada en Zaragoza del 3 al 5 de febrero 2020.

Published
2020

18. Reflexiones de una futura docente

Author

Galiana Cameo, María and Cascarosa Salillas, Esther

Abstract

Realizar un aprendizaje guiado para que el alumno conozca en profundidad el significado científico de ciertos contenidos teóricos, puede ayudarle a minimizar errores de concepto posteriores, evitando que solamente recurra a su capacidad memorística y fomentando el desarrollo de su razonamiento.En relación con la labor del docente, a lo largo de todo este trabajo se pone de manifiesto la gran cantidad de tiempo y esfuerzo que es necesario invertir en la preparación de una asignatura siguiendo esta metodología. Para ello, es fundamental disponer de un elevado grado de motivación, que sin duda se verá reflejado en el desarrollo de las sesiones y que también se transmitirá al alumnado.En definitiva, esta profesión es claramente vocacional y, por ello, la primera persona que debe sentir y demostrar entusiasmo por la enseñanza es el propio docente. De esta forma, podrá ayudar al alumno a que conforme una visión crítica de la realidad y resuelva problemas cotidianos, potenciando sus capacidades para que sea una persona competente y crítica en nuestra sociedad.

Published
2019

19. Variation on the π‐Acceptor Ligand within a RhI−N‐Heterocyclic Carbene Framework: Divergent Catalytic Outcomes for Phenylacetylene‐Methanol Transformations.

Author

Galiana‐Cameo, María, Passarelli, Vincenzo, Pérez‐Torrente, Jesús J., Di Giuseppe, Andrea, and Castarlenas, Ricardo

Subjects
*ENOL ethers, *CARBONYLATION, *RHODIUM, *RHODIUM catalysts, *POLYMERIZATION, *DIMERIZATION, *LIGANDS (Chemistry), *CARBENE synthesis
Abstract

A series of neutral and cationic rhodium complexes bearing IPr {IPr=1,3‐bis‐(2,6‐diisopropylphenyl)imidazolin‐2‐carbene} and π‐acceptor ligands are reported. Cationic species [Rh(η4‐cod)(IPr)(NCCH3)]+ and [Rh(CO)(IPr)(L)2]+ (L=pyridine, CH3CN) were obtained by chlorido abstraction in suitable complexes, whereas the cod‐CO derivative [Rh(η4‐cod)(IPr)(CO)]+ was formed by the carbonylation of [Rh(η4‐cod)(IPr)(NCCH3)]+. Alternatively, neutral derivatives of type RhCl(IPr)(L)2 {L=tBuNC or P(OMe)3} can be accessed from [Rh(μ‐Cl)(η2‐coe)(IPr)]2. In addition, the mononuclear species Rh(CN)(η4‐cod)(IPr) was prepared by cyanide‐chlorido anion exchange, which after carbonylation afforded the unusual trinuclear compound [Rh{1κC,2κN‐(CN)}(CO)(IPr)]3. Divergent catalytic outcomes in the phenylacetylene‐methanol transformations have been observed. Thus, enol ethers, arisen from hydroalkoxylation of the alkyne, were obtained with neutral Rh−CO catalyst precursors whereas dienol ethers were formed with cationic catalysts. Variable amounts of alkyne dimerization, cyclotrimerization or polymerization products were obtained in the absence of a strong π‐acceptor ligand on the catalyst. [ABSTRACT FROM AUTHOR]

Published
2021
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21. Studying the mechanism of action of novel stabilizing compounds of phenylalanine hydroxylase

Author

Conde-Giménez, María, Salillas, Sandra, Galano-Frutos, Juan J., Galiana-Cameo, María, Díaz de Villegas, María D., and Sancho, Javier

Abstract

Resumen del póster presentado a la VIII National Congress of the Institute for Biocomputation and Physics of Complex Systems (BIFI), celebrado en Zaragoza (España) del 31 de enero al 2 de febrero de 2017.

Published
2017

24. Rhodium-NHC-Catalyzed gem-Specific O-Selective Hydropyridonation of Terminal Alkynes.

Author

Galiana-Cameo M, Romeo R, Urriolabeitia A, Passarelli V, Pérez-Torrente JJ, Polo V, and Castarlenas R

Abstract

The dinuclear complex [Rh(μ-Cl)(η 2 -coe)(IPr)] 2 is an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations support a hydride-free pathway entailing intramolecular oxidative protonation of a π-alkyne by a κ 1 N-hydroxypyridine ligand. Subsequent O-nucleophilic attack on a metallacyclopropene species affords an O-alkenyl-2-oxypyridine chelate rhodium intermediate as the catalyst resting state. The release of the alkenyl ether is calculated as the rate-determining step., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Published
2022
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25. Rhodium(I)-NHC Complexes Bearing Bidentate Bis-Heteroatomic Acidato Ligands as gem-Selective Catalysts for Alkyne Dimerization.

Author

Galiana-Cameo M, Borraz M, Zelenkova Y, Passarelli V, Lahoz FJ, Pérez-Torrente JJ, Oro LA, Di Giuseppe A, and Castarlenas R

Abstract

A series of Rh(κ 2 -BHetA)(η 2 -coe)(IPr) complexes bearing 1,3-bis-hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reaction of the dinuclear precursor [Rh(μ-Cl)(IPr)(η 2 -coe)] 2 with the corresponding anionic BHetA species. The Rh I -NHC-BHetA compounds catalyze the dimerization of aryl alkynes, showing excellent selectivity for the head-to-tail enynes. Among them, the acetanilidato-based catalyst has shown an outstanding catalytic performance reaching unprecedented TOF levels of 2500 h -1 with complete selectivity for the gem-isomer. Investigation of the reaction mechanism supports a non-oxidative pathway in which the BHetA ligand behaves as proton shuttle through intermediate κ 1 -HBHetA species. However, in the presence of pyridine as additive, the identification of the common Rh III H(C≡CPh) 2 (IPr)(py) 2 intermediate gives support for an alternative oxidative route., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Published
2020
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