123 results on '"Antonio Leyva-Pérez"'
Search Results
2. One-Pot Synthesis of Terminal Alkynes from Alkenes
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Cristina Bilanin, Amravati S. Singh, Lluis Martínez-Belenguer, and Antonio Leyva-Pérez
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Chemistry ,QD1-999 - Published
- 2024
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Catalog
3. Soluble individual metal atoms and ultrasmall clusters catalyze key synthetic steps of a natural product synthesis
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Silvia Rodríguez-Nuévalos, Miguel Espinosa, and Antonio Leyva-Pérez
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Chemistry ,QD1-999 - Abstract
Abstract Metal individual atoms and few-atom clusters show extraordinary catalytic properties for a variety of organic reactions, however, their implementation in total synthesis of complex organic molecules is still to be determined. Here we show a 11-step linear synthesis of the natural product (±)-Licarin B, where individual Pd atoms (Pd1) catalyze the direct aerobic oxidation of an alcohol to the carboxylic acid (steps 1 and 6), Cu2-7 clusters catalyze carbon-oxygen cross couplings (steps 3 and 8), Pd3-4 clusters catalyze a Sonogashira coupling (step 4) and Pt3-5 clusters catalyze a Markovnikov hydrosylilation of alkynes (step 5), as key reactions during the synthetic route. In addition, the new synthesis of Licarin B showcases an unexpected selective alkene hydrogenation with metal-free NaBH4 and an acid-catalyzed intermolecular carbonyl-olefin metathesis as the last step, to forge a trans-alkene group. These results, together, open new avenues in the use of metal individual atoms and clusters in organic synthesis, and confirm their exceptional catalytic activity in late stages during complex synthetic programmes. more...
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- 2024
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4. In-Flow Heterogeneous Triplet–Triplet Annihilation Upconversion
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Jorge Castellanos-Soriano, Francisco Garnes-Portolés, M. Consuelo Jiménez, Antonio Leyva-Pérez, and Raúl Pérez-Ruiz
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Physical and theoretical chemistry ,QD450-801 - Published
- 2024
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5. HY zeolite catalyzes the ortho–methylation of 1–naphthol
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Matea Bačić, Maria Tejeda–Serrano, Yongkun Zheng, Judit Oliver–Meseguer, and Antonio Leyva–Pérez
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Zeolites ,1–naphthol ,Methylation reaction ,Heterogeneous catalysis ,Vitamin K3 ,Materials of engineering and construction. Mechanics of materials ,TA401-492 ,Industrial electrochemistry ,TP250-261 - Abstract
The selective ortho–alkylation of 1–naphthol with methanol is carried out over various commercially available acid solid catalysts under relatively mild reaction conditions (
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- 2024
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6. Ag2(0) dimers within a thioether-functionalized MOF catalyze the CO2 to CH4 hydrogenation reaction
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Yongkun Zheng, Nuria Martín, Mercedes Boronat, Jesús Ferrando-Soria, Marta Mon, Donatella Armentano, Emilio Pardo, and Antonio Leyva-Pérez
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Medicine ,Science - Abstract
Abstract Ultrasmall silver clusters in reduced state are difficult to synthesize since silver atoms tend to rapidly aggregate into bigger entities. Here, we show that dimers of reduced silver (Ag2) are formed within the framework of a metal–organic framework provided with thioether arms in their walls (methioMOF), after reduction with NaBH4 of the corresponding Ag+-methioMOF precursor. The resulting Ag2-methioMOF catalyzes the methanation reaction of carbon dioxide (CO2 to CH4 hydrogenation reaction) under mild reaction conditions (1 atm CO2, 4 atm H2, 140 °C), with production rates much higher than Ag on alumina and even comparable to the state-of-the-art Ru on alumina catalyst (Ru–Al2O3) under these reaction conditions, according to literature results. more...
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- 2023
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7. Parts–per–million of ruthenium catalyze the selective chain–walking reaction of terminal alkenes
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Sergio Sanz-Navarro, Marta Mon, Antonio Doménech-Carbó, Rossella Greco, Jorge Sánchez-Quesada, Estela Espinós-Ferri, and Antonio Leyva-Pérez
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Science - Abstract
The chain-walking of terminal alkenes is an industrially relevant reaction. Here, the authors show that part-per-million amounts of a variety of ruthenium compounds catalyze the reaction in yields and selectivity up to >99%, without any solvent or additive. more...
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- 2022
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8. Acid Catalysis with Alkane/Water Microdroplets in Ionic Liquids
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Rossella Greco, Vicent Lloret, Miguel Ángel Rivero-Crespo, Andreas Hirsch, Antonio Doménech-Carbó, Gonzalo Abellán, and Antonio Leyva-Pérez
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Chemistry ,QD1-999 - Published
- 2021
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9. Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework
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Marta Mon, Rosaria Bruno, Sergio Sanz-Navarro, Cristina Negro, Jesús Ferrando-Soria, Lucia Bartella, Leonardo Di Donna, Mario Prejanò, Tiziana Marino, Antonio Leyva-Pérez, Donatella Armentano, and Emilio Pardo more...
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Science - Abstract
Elucidation of the chemical structure of natural products constitutes one of the main challenges in Natural Sciences. Here, the authors show that an amino acid-based metal–organic framework exhibits hydrolase-like catalytic activity and crystallographic determination of the resulting products. more...
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- 2020
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10. Few layer 2D pnictogens catalyze the alkylation of soft nucleophiles with esters
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Vicent Lloret, Miguel Ángel Rivero-Crespo, José Alejandro Vidal-Moya, Stefan Wild, Antonio Doménech-Carbó, Bettina S. J. Heller, Sunghwan Shin, Hans-Peter Steinrück, Florian Maier, Frank Hauke, Maria Varela, Andreas Hirsch, Antonio Leyva-Pérez, and Gonzalo Abellán more...
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Science - Abstract
Group 15 elements in zero oxidation state, also called pnictogens, are rarely used in catalysis due to the difficulties in preparation. Here, the authors report on the synthesis of highly exfoliated, few layer 2D phosphorene and antimonene in zero oxidation state, and their use as efficient catalysts for the alkylation of nucleophiles with esters. more...
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- 2019
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11. Publisher Correction: Hydrolase–like catalysis and structural resolution of natural products by a metal–organic framework
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Marta Mon, Rosaria Bruno, Sergio Sanz-Navarro, Cristina Negro, Jesús Ferrando-Soria, Lucia Bartella, Leonardo Di Donna, Mario Prejanò, Tiziana Marino, Antonio Leyva-Pérez, Donatella Armentano, and Emilio Pardo more...
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Science - Abstract
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
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- 2020
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12. Exploring the Role of Amino Acid-Derived Multivariate Metal–Organic Frameworks as Catalysts in Hemiketalization Reactions
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Cristina Negro, Sergio Sanz-Navarro, Antonio Leyva-Pérez, Donatella Armentano, Jesús Ferrando-Soria, and Emilio Pardo
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Inorganic Chemistry ,Physical and Theoretical Chemistry - Published
- 2023
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13. MOF-Triggered Synthesis of Subnanometer Ag02 Clusters and Fe3+ Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions
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Estefanía Tiburcio, Yongkun Zheng, Cristina Bilanin, Juan Carlos Hernández-Garrido, Alejandro Vidal-Moya, Judit Oliver-Meseguer, Nuria Martín, Marta Mon, Jesús Ferrando-Soria, Donatella Armentano, Antonio Leyva-Pérez, and Emilio Pardo more...
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Colloid and Surface Chemistry ,General Chemistry ,Biochemistry ,Catalysis - Published
- 2023
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14. Indomuscone-Based Sterically Encumbered Phosphines as Ligands for Palladium-Catalyzed Reactions
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Francisco Garnes-Portolés, Sergio Sanz-Navarro, Jordi Ballesteros-Soberanas, Ana Collado-Pérez, Jorge Sánchez-Quesada, Estela Espinós-Ferri, and Antonio Leyva-Pérez
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Organic Chemistry - Published
- 2023
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15. Electron-Poor Phosphines Enable the Selective Semihydrogenation Reaction of Alkynes with Pd on Carbon Catalysts
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Jordi Ballesteros-Soberanas, Antonio Leyva-Pérez, and Ministerio de Ciencia e Innovación (España)
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General Materials Science ,Physical and Theoretical Chemistry - Abstract
An alternative to the Lindlar catalyst for the semihydrogenation reaction of alkynes to alkenes is of high interest. Here we show that palladium on carbon (Pd/C), i.e., a widely available supported Pd catalyst, is converted from an unselective to a chemoselective catalyst during the semihydrogenation reaction of alkynes, after the addition of catalytic amounts of commercially available electron-poor phosphines. The catalytic activity is ≤7 times greater, and the selectivity is comparable to that of the industrial benchmark Lindlar catalyst., J.B.-S. is thankful for “La Caixa” Foundation Grant 100010434 (code LCF/BQ/DI19/11730029). This work is part of Projects PID2020-115100GB-I00 (funded by MCIN/AEI/10.13039/501100011033MICIIN), “Severo Ochoa” SEV-2016-0683 (funded by MINECO), and “La Caixa” Foundation Grant 100010434 (code LCF/BQ/DI19/11730029). Financial support by the Severo Ochoa center of excellence program (CEX2021-001230-S) is also gratefully acknowledged. more...
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- 2023
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16. Intimate ruthenium–platinum nanoalloys supported on carbon catalyze the hydrogenation and one-pot hydrogenation-coupling reaction of oxidized amino derivatives
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Miguel A. Rivero-Crespo, Paula Rubio-Marqués, Juan Carlos Hernández-Garrido, Marta Mon, Judit Oliver-Meseguer, and Antonio Leyva-Pérez
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Catalysis - Abstract
Intimate, recyclable, solid-supported ruthenium–platinum nanoalloys catalyse the one-pot hydrogenation-coupling reaction of oxidized amino derivatives.
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- 2023
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17. Metal–organic frameworks as chemical nanoreactors for the preparation of catalytically active metal compounds
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Paula Escamilla, Walter D. Guerra, Antonio Leyva-Pérez, Donatella Armentano, Jesús Ferrando-Soria, and Emilio Pardo
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Materials Chemistry ,Metals and Alloys ,Ceramics and Composites ,General Chemistry ,Catalysis ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials - Abstract
Since the emergence of metal-organic frameworks (MOFs), a myriad of thrilling properties and applications, in a wide range of fields, have been reported for these materials, which mainly arise from their porous nature and rich host-guest chemistry. However, other important features of MOFs that offer great potential rewards have been only barely explored. For instance, despite the fact that MOFs are suitable candidates to be used as chemical nanoreactors for the preparation, stabilization and characterization of unique functional species, that would be hardly accessible outside the functional constrained space offered by MOF channels, only very few examples have been reported so far. In particular, we outline in this feature recent advances in the use of highly robust and crystalline oxamato- and oxamidato-based MOFs as reactors for the more...
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- 2023
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18. A Career in Catalysis: Avelino Corma
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Mercedes Boronat, Maria J. Climent, Patricia Concepción, Urbano Díaz, Hermenegildo García, Sara Iborra, Antonio Leyva-Pérez, Lichen Liu, Agustin Martínez, Cristina Martínez, Manuel Moliner, Joaquín Pérez-Pariente, Fernando Rey, Enrique Sastre, Pedro Serna, and Susana Valencia more...
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General Chemistry ,Catalysis - Abstract
As one of the most influential scientists in the field of heterogeneous catalysis and materials science, Prof. Avelino Corma has made significant contributions in many diverse fields, spanning over solid catalysts for petrochemistry, solid catalysts for production of fine chemicals, synthesis of microporous and mesoporous materials, development of inorganic-organic hybrid materials, supported metal catalysts (from isolated metal atoms to nanoclusters and nanoparticles) and photochemistry with solid materials. These experimental approaches are complemented with characterization of solid materials with advanced spectroscopy and microscopy techniques as well as theoretical calculations/modeling. The aim of this Account is to overview Avelino's distinguished scientific career and highlight the most remarkable achievements made in his research activities during >40 years. We attempt to show the evolution of Avelino's research topics in his group throughout his career and the approaches that Avelino has chosen to tackle the challenges encountered. The research paradigm developed by Avelino and his team can be inspiring to the researchers in the field of materials science who are striving to translate the knowledge generated in fundamental studies into practical applications for addressing the new scientific challenges encountered in building a sustainable world. more...
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- 2022
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19. Mizoroki–Heck Macrocyclization Reactions at 1 M Concentration Catalyzed by Sub‐nanometric Palladium Clusters
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Francisco Garnes–Portolés, Estíbaliz Merino, and Antonio Leyva–Pérez
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General Energy ,General Chemical Engineering ,Environmental Chemistry ,General Materials Science - Published
- 2023
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20. Single Atom and Metal Cluster Catalysts in Organic Reactions: From the Solvent to the Solid
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Judit Oliver‐Meseguer and Antonio Leyva‐Pérez
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Inorganic Chemistry ,Organic Chemistry ,Physical and Theoretical Chemistry ,Catalysis - Published
- 2023
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21. Supported Metal Single Atom Thermocatalysts for<scp>CC, CSi</scp>, and<scp>CB</scp>Bond–Forming (Coupling) Reactions and Biomedical Applications
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Rossella Greco, Marta Mon, and Antonio Leyva–Pérez
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- 2022
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22. Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)2 catalyst in a metal–organic framework
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Cristina Negro, Cristina Bilanin, Xiaoni Qu, Judit Oliver-Meseguer, Jesús Ferrando-Soria, Antonio Leyva-Pérez, Donatella Armentano, Emilio Pardo, and Leyva–Pérez, Antonio
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Materials Chemistry ,Metals and Alloys ,Ceramics and Composites ,General Chemistry ,Catalysis ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials - Abstract
Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)2 is used in solution or anchored in a metal–organic framework (MOF). The chemical mechanism depends on the electronic profile of alkene substituents when the vanadyl complex is used in the homogenous phase. However, confinement effects imparted by MOF channels allow gaining control of the chemoselectivity toward the dehydrogenation product. more...
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- 2022
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23. Zeolites catalyze the halogen exchange reaction of alkyl halides
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Paloma Mingueza-Verdejo, Juan Carlos Hernández-Garrido, Alejandro Vidal-Moya, Judit Oliver-Meseguer, Antonio Leyva-Pérez, Ministerio de Ciencia e Innovación (España), and Leyva, Antonio
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Catalysis - Abstract
Simple aluminosilicates, including NaX and NaY zeolites, catalyze the selective halogen exchange reaction between two different alkyl organohalides, either in batch or in flow, without any additive or solvent, by simply heating at 130 °C and with, Financial support of the Spanish projects PID2020-115100GB-I00 and PID2019-107578GA-I00, the Juan de la Cierva Program (contract number IJC2018-036514-I) and the Severo Ochoa Centre of Excellence Program CEX2021-001230-S (funded by MCIINN except for the former, funded by MCIN/AEI/10.13039/501100011033MICIIN) is acknowledged. Financial support of the Generalitat Valenciana, Grupos Emergentes Program (GV/2021/138) is also acknowledged. P.M. thanks ITQ for a contract. The AC-STEM data were obtained at the DME–UCA node of the Spanish Unique Scientific and Technological Infrastructure (ICTS) of Electron Microscopy of Materials ELECMIM. more...
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- 2023
24. A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes
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Alejandro Lumbreras‐Teijeiro, Matea Bacic, Judit Oliver‐Meseguer, Antonio Leyva‐Pérez, and Ministerio de Ciencia e Innovación (España)
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Organic Chemistry ,General Chemistry ,Catalysis - Abstract
The engagement in tandem of well-known organic reactions such as the Pd-catalyzed Sonogashira cross-coupling reaction, nucleophilic substitution and elimination reactions, enables the synthesis of otherwise difficult to obtain linear dienynes, in moderate to high yields. This retrosynthetic approach opens new ways to prepare highly conjugated alkenes and alkynes. Furthermore, ionic liquids are suitable solvents to perform the cascade reaction and recycle the metal catalysts., This work was supported by the MICINN (Spain) (Project PID2020-115100GB−I00). The work has also been funded by Generalitat Valenciana, Grupos Emergentes (GV/2021/138). A. L.-T. thanks the MICINN for the concession of the FPI grant PRE2020-093338 (through SEV-2016-0683-20-3). J. O.-M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018-036514-I). M. B. thanks ITQ for the concession of a contract. more...
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- 2022
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25. Synthesis of Dehydromuscone by an Alkene Metathesis Macrocyclization Reaction at 02 M Concentration
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Antonio Leyva-Pérez, Francisco Garnes-Portolés, Jorge Sánchez-Quesada, Estela Espinós-Ferri, and Ministerio de Ciencia e Innovación (España)
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Organic Chemistry - Abstract
The industrial fragrance compound dehydromuscone was synthesized in five linear steps and 19% overall yield. The synthesis features a highly efficient nondiluted ring-closing metathesis macrocyclization reaction as a key step that proceeds at a 0.2 M concentration in the presence of 0.1 mol% Nitro-Grela catalyst. The synthesis employs commercially available linear starting materials and is shorter by at least two steps than the current industrial synthesis route., Financial support by the project PID2020-115100GB-I00 (funded by Spanish MCIINN, MCIN/AEI/10.13039/ 501100011033MICIIN) is acknowledged. more...
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- 2022
26. Parametrization of Catalytic Organic Reactions with Convex Hammett
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Jordi Ballesteros-Soberanas, Cristina Bilanin, Antonio Leyva-Pérez, Ministerio de Ciencia e Innovación (España), and Leyva, Antonio
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Cultural Studies ,styrene coupling ,History ,Hammett plot ,metal clusters ,Literature and Literary Theory ,catalysis ,parametrization ,semi-hydrogenation of alkynes ,organic synthesis ,substrate scope - Abstract
Quantification is essential to fairly compare between synthetic reactions in chemistry. Here we propose two new parameters called “adapted sensitivity constant” (ρadap) and “substrate electronics adaptability” (SEA), easily obtainable from Hammett plots, to assess the ability of a (catalytic) reaction to transform substrates with opposing electronics. These new parameters allow one to list reactions, catalyzed or not, as a function of substrate scope., Financial support by the projects PID2020-115100GB-I00 (funded by Spanish MCIINN, MCIN/AEI/10.13039/501100011033MICIIN) and “La Caixa” Foundation grant (ID 100010434, code LCF/BQ/DI19/11730029) is acknowledged. C.B. thanks ITQ for a contract. more...
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- 2022
27. Cytotoxic sub-nanometer aqueous platinum clusters as potential antitumoral agents
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Rossella Greco, Guillermo García-Lainez, Judit Oliver-Meseguer, Carlo Marini, Irene Domínguez, Miguel López-Haro, Juan Carlos Hernández-Garrido, José Pedro Cerón-Carrasco, Inmaculada Andreu, Antonio Leyva-Pérez, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia e Innovación (España) more...
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General Engineering ,General Materials Science ,Bioengineering ,General Chemistry ,Atomic and Molecular Physics, and Optics - Abstract
Ligand-free sub-nanometer metal clusters (MCs) of Pt, Ir, Rh, Au and Cu, are prepared here in neat water and used as extremely active (nM) antitumoral agents for HeLa and A2870 cells. The preparation just consists of adding the biocompatible polymer ethylene-vinyl alcohol (EVOH) to an aqueous solution of the corresponding metal salt, to give liters of a MC solution after filtration of the polymer. Since the MC solution is composed of just neat metal atoms and water, the intrinsic antitumoral activity of the different sub-nanometer metal clusters can now fairly be evaluated. Pt clusters show an IC of 0.48 μM for HeLa and A2870 cancer cells, 23 times higher than that of cisplatin and 1000 times higher than that of Pt NPs, and this extremely high cytotoxicity also occurs for cisplatin-resistant (A2870 cis) cells, with a resistance factor of 1.4 (IC = 0.68 μM). Rh and Ir clusters showed an IC ∼ 1 μM. Combined experimental and computational studies support an enhanced internalization and cytotoxic activation., This work was supported by MINECO (Spain, Projects CTQ 2017-86735-P [AEI/FEDER, UE], PID2020-115010RB-I00, BEAGAL 18/00211, MAT2017-87579-R, IJC2018-036514-I and SEV-2016-0683). Financial support by the project PID2020-115100GB-I00 (funded by Spanish MCIINN, MCIN/AEI/10.13039/501100011033MICIIN) is acknowledged. more...
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- 2022
28. Acid and Base Water Coexists in a Micro-Structured Ionic Liquid and Catalyzes Organic Reactions in One-Pot
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Antonio Leyva‐Pérez, Cristina Bilanin, Matea Bacic, Rossella Greco, and Ministerio de Ciencia e Innovación (España)
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Inorganic Chemistry ,Organic Chemistry ,Physical and Theoretical Chemistry ,Catalysis - Abstract
The most paradigmatic example of antagonist chemical species are protons and hydroxyls, and their coexistence in a liquid system is of high interest. Here we show that commercial ionic liquids stabilize microdroplets of water with pH14, concomitantly and without any additive, and that this micro-structured liquid medium catalyzes organic reactions in one-pot., Financial support by the project PID2020-115100GB-I00 (funded by Spanish MCIINN, MCIN/AEI/10.13039/501100011033MICIIN) is acknowledged. C. B. and R. G. thanks ITQ for a contract. We thank José M. Coll-Marqués (UV) for helping us with microfluorescence measurements. more...
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- 2022
29. Cover Feature: Acid and Base Water Coexists in a Micro‐Structured Ionic Liquid and Catalyzes Organic Reactions in One‐Pot (ChemCatChem 19/2022)
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Antonio Leyva‐Pérez, Cristina Bilanin, Matea Bacic, and Rossella Greco
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Inorganic Chemistry ,Organic Chemistry ,Physical and Theoretical Chemistry ,Catalysis - Published
- 2022
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30. Highly Efficient MOF-Driven Silver Subnanometer Clusters for the Catalytic Buchner Ring Expansion Reaction
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Estefanía Tiburcio, Yongkun Zheng, Marta Mon, Nuria Martín, Jesús Ferrando−Soria, Donatella Armentano, Antonio Leyva−Pérez, Emilio Pardo, Ministerio de Ciencia e Innovación (España), Generalitat Valenciana, and European Research Council more...
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Inorganic Chemistry ,Physical and Theoretical Chemistry - Abstract
The preparation of novel efficient catalysts-that could be applicable in industrially important chemical processes-has attracted great interest. Small subnanometer metal clusters can exhibit outstanding catalytic capabilities, and thus, research efforts have been devoted, recently, to synthesize novel catalysts bearing such active sites. Here, we report the gram-scale preparation of Ag2subnanometer clusters within the channels of a highly crystalline three-dimensional anionic metal-organic framework, with the formula [Ag2]@AgNa{Ni[Cu(Mempba)]}·48HO [Mempba= N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. The resulting crystalline solid catalyst-fully characterized with the help of single-crystal X-ray diffraction-exhibits high catalytic activity for the catalytic Buchner ring expansion reaction., This work was supported by the Ministero dell’Università e della Ricerca (Italy), the MICIIN (Spain) (projects PID2020-115100GB-I00, PID2019-104778GB-I00 and Excellence Unit “Maria de Maeztu” CEX2019-000919-M), and the Generalitat Valenciana (project PROMETEO/2021/054). Thanks are also extended to the Ramon y Cajal Program (RYC2019-027940-I) (J. F.-S.) and the Diamond Light Source for the awarded beamtime and provision of synchrotron radiation facilities (proposal no. CY22411-1). We particularly acknowledge Dr David Allan and Sarah Barnett for their assistance at the I19 beamline. E.P. acknowledges the financial support of the European Research Council under the European Union’s Horizon 2020 research and innovation programme/ERC grant agreement no 814804, MOF-reactors. M.M. thanks MICIIN from a contract under the Juan de la Cierva program (FJC2019-040523-I). Y.Z. thanks the China Scholarship Council (CSC no: 202009350009) for a Ph.D. fellowship. more...
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- 2022
31. Crystallographic Visualization of a Double Water Molecule Addition on a Pt 1 ‐MOF during the Low‐temperature Water‐Gas Shift Reaction
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Emilio Pardo, Jesús Ferrando-Soria, Antonio Leyva-Pérez, Donatella Armentano, Cristina Bilanin, and Estefanía Tiburcio
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Materials science ,Aigua Química ,Metal-organic framework ,Single atom catalyst ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,7. Clean energy ,Catalysis ,Water-gas shift reaction ,Inorganic Chemistry ,Catàlisi ,Molecule ,Physical and Theoretical Chemistry ,Platinum ,Water gas shift reaction ,Crystallography ,010405 organic chemistry ,Organic Chemistry ,0104 chemical sciences ,Visualization ,chemistry ,Cristalls - Abstract
[EN] The low-temperature water-gas shift reaction (WGSR, CO+H2O H-2+CO2) is considered a very promising reaction -candidate for fuel cells- despite an efficient and robust catalyst is still desirable. One of the more prominent catalysts for this reaction is based on single Pt atoms (Pt-1) on different supports, which are supposed to manifold the reaction by the accepted mechanism for the general WGSR, i. e. by addition of one H2O molecule to CO, with generation of CO2 and H-2. Here we show, experimentally, that not one but two H2O molecules are added to CO on the Pt-1 catalyst, as assessed by a combination of reactivity experiments with soluble Pt catalysts, kinetic and spectroscopic measurements, and finally by in-operando single crystal X-ray diffraction on a Pt-1-MOF, to visualize the formation of the hemiacetal intermediate on the solid catalytic site. These results confirm our previous DFT predictions and provide a paradigmatic shift in the assumed mechanism of the WGSR, which may open the debate if two H2O molecules are recurrently added during the WGSR, not only for Pt-1 catalysts but also for other metal catalysts., This work was supported by the Ministero dell'Istruzione, dell'Universita e della Ricerca (Italy) and the Ministerio de Ciencia e Innovacion (Spain) (Projects PID2019-104778GB-I00 and CTQ2017-86735-P and the excellence units "Severo Ochoa" SEV-2016-0683 and "Maria de Maeztu" CEX2019-000919-M). C. B. and E. T. thank ITQ and MINECO for the concession of fellowships. Thanks are extended to the "2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011" (J. F.-S.). D.A. acknowledges the financial support of the Fondazione CARIPLO / "Economia Circolare: ricerca per un futuro sostenibile" 2019, Grant number: 2019-2090, MOCA. We thank to Dr. R. Adam, Dr. J. Oliver-Meseguer and J. C. Arango for their help. E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme / ERC Grant Agreement No 814804, MOF-reactors. We acknowledge Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities with dosing gas cell and thank Dr Mark Warren for his assistance at I19 beamline (Proposal number MT18768-2). more...
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- 2020
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32. Parts-Per-Million of Soluble Pd
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Jordi, Ballesteros-Soberanas, Jose A, Carrasco, and Antonio, Leyva-Pérez
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The synthesis of
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- 2022
33. Parts-Per-Million of Soluble Pd0 Catalyze the Semi-Hydrogenation Reaction of Alkynes to Alkenes
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Jordi Ballesteros-Soberanas, Jose A. Carrasco, Antonio Leyva-Pérez, Ministerio de Ciencia e Innovación (España), and Leyva–Pérez, Antonio
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Organic Chemistry - Abstract
The synthesis of cis-alkenes is industrially carried out by selective semi-hydrogenation of alkynes with complex Pd catalysts, which include the Lindlar catalyst (PdPb on CaCO3) and c-Pd/TiS (colloidal ligand-protected Pd nanoparticles), among others. Here, we show that Pd0 atoms are generated from primary Pd salts (PdCl2, PdSO4, Pd(OH)2, PdO) with H2 in alcohol solutions, independently of the alkyne, to catalyze the semi-hydrogenation reaction with extraordinarily high efficiency (up to 735 s–1), yield (up to 99%), and selectivity (up to 99%). The easy-to-prepare Pd0 species hold other potential catalytic applications., This work is part of the project PID2020-115100GB-I00 funded by MCIN/AEI/10.13039/501100011033MICIIN and “Severo Ochoa” SEV-2016-0683 funded by MINECO. more...
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- 2022
34. Epoxidation
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Cristina, Negro, Cristina, Bilanin, Xiaoni, Qu, Judit, Oliver-Meseguer, Jesús, Ferrando-Soria, Antonio, Leyva-Pérez, Donatella, Armentano, and Emilio, Pardo
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Propanols ,Epoxy Compounds ,Catalysis ,Metal-Organic Frameworks - Abstract
Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)
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- 2022
35. Mixed component metal-organic frameworks: Heterogeneity andcomplexity at the service of application performances
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Emilio Pardo, Jesús Ferrando-Soria, Marta Viciano-Chumillas, Xiangyu Liu, Donatella Armentano, Antonio Leyva-Pérez, Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España), and Leyva, Antonio more...
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Inorganic Chemistry ,Service (systems architecture) ,010405 organic chemistry ,Chemistry ,Component (UML) ,Materials Chemistry ,Nanotechnology ,Metal-organic framework ,Physical and Theoretical Chemistry ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences - Abstract
The synthesis of mixed-component metal-organic frameworks (MOFs) –including multivariate MOFs (MTV-MOFs), multicomponent MOFs, mixed-metals MOFs and mixed-ligands and metals MOFs– is becoming a very active research field. This is mainly based on the unique possibilities these materials offer to incorporate multiple functionalities and in how this heterogenity and complexity is translated in unexpected properties, which are not just the sum of each component. This review critically encompasses the progress made in this field, covering the synthetic approaches, and specially focusing on the current reported applications –such as gas storage and separation, catalysis, luminescence, conductivity, biological ones and water remediation. It also raises, as a perspective, some of the challenges the field has to overcome to reach their full-potential, and through two applications –(bio)enzymatic catalysis and synthesis of heterometallic subnanometric clusters and nanoparticles–, as exemplary cases, present some promising ways to take advantage of the intrinsic properties of mixed-components MOFs to make a breakthrough on the respective fields of application., This work was supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy), the Natural Science Foundation of Ningxia Province (China) (2020AAC02005) and the MINECO (Spain) (Projects PID2019–104778GB–I00, CTQ 2017–86735–P, RTC–2017–6331–5, Severo Ochoa program SEV–2016–0683 and Excellence Unit “Maria de Maeztu” CEX2019–000919–M). D.A. acknowledges the financial support of the Fondazione CARIPLO / “Economia Circolare: ricerca per un futuro sostenibile” 2019, Project code: 2019–2090, MOCA. Thanks are also extended to the “2019 Post–doctoral Junior Leader–Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011)”, the “Ramon y Cajal Programme” and “Subvenciones concedidas a la excelencia científica de juniors investigadores, SEJI/2020/034” (J. F.–S.). E.P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation programme / ERC Grant Agreement No 814804, MOF–reactors. more...
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- 2022
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36. Selective semi-hydrogenation of internal alkynes catalyzed by Pd–CaCO3 clusters
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Jordi Ballesteros-Soberanas, Juan Carlos Hernández-Garrido, José Pedro Cerón-Carrasco, Antonio Leyva-Pérez, Ministerio de Ciencia e Innovación (España), Ballesteros-Soberanas, Jordi [0000-0002-6938-2575], Leyva, Antonio [0000-0003-1063-5811], Ballesteros-Soberanas, Jordi, and Leyva, Antonio more...
- Subjects
Physical and Theoretical Chemistry ,Catalysis - Abstract
The de-novo synthesis of soluble or solid-supported Pd-(CaCO) clusters (n = 2–13) and their high catalytic activity for the semi-hydrogenation of internal alkynes compared to terminal alkynes, is presented. Mechanistic studies show that this reactivity, i.e. internal alkynes more reactive than terminal alkynes, comes from the higher electrophilicity of the Pd-(CaCO) cluster compared to the nanoparticulated Lindlar catalyst, which unveils the advantages of isolating the minimum catalytic unit of a solid catalyst. Translating solid active sites into soluble catalysts turns around the classical approach and constitutes a paradigmatic shift in catalyst design., This work is part of the projects PID2020–115100GB–I00 and PID2019–107578GA–I00, both funded by MCIN/AEI/10.13039/501 100011033MICIIN, and ‘‘La Caixa” Foundation grant (ID 100010434), code LCF/BQ/DI19/11730029. more...
- Published
- 2022
37. Nanotitania catalyzes the chemoselective hydration and alkoxylation of epoxides
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María Tejeda–Serrano, Aarón Martínez–Castelló, Jordi Ballesteros–Soberanas, Antonio Leyva–Pérez, Judit Oliver–Meseguer, Ministerio de Ciencia e Innovación (España), and La Caixa
- Subjects
Primary (chemistry) ,Chemistry ,Process Chemistry and Technology ,Ethoxylation ,1,4-dioxanones ,Catalysis ,chemistry.chemical_compound ,Glycols ,Epoxides ,Nanotitania ,Alkoxy group ,Propoxylation ,Organic chemistry ,Phenols ,Physical and Theoretical Chemistry ,Tertiary alcohols ,Alkoxylation ,Vacancies - Abstract
[EN] Glycols and ethoxy- and propoxy-alcohols are fundamental chemicals in industry, with annual productions of millions of tons, still manufactured in many cases with corrosive and unrecoverable catalysts such as KOH, amines and BF3 center dot OEt2. Here we show that commercially available, inexpensive, non-toxic, solid and recyclable nanotitania catalyzes the hydration and alkoxylation of epoxides, with water and primary and secondary alcohols but not with phenols, carboxylic acids and tertiary alcohols. In this way, the chemoselective synthesis of different glycols and 1,4-dioxanones, and the implementation of nanotitania for the production in-flow of glycols and alkoxylated alcohols, has been achieved. Mechanistic studies support the key role of vacancies in the nano-oxide catalyst., A.L.-P. thanks the MICIIN (project code PID2020-115100GB-I00) for financial support. J.O.-M. thanks the Juan de la Cierva Program for the concession of a contract (IJC2018-036514-I). J.B.-S. thanks La Caixa Foundation grant (ID 100010434), code LCF/BQ/DI19/11730029. more...
- Published
- 2021
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38. Gitteröffnung durch reduktive kovalente Volumen‐Funktionalisierung von schwarzem Phosphor
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Herwig Peterlik, Christian Papp, Haiko Wittkämper, Andreas Görling, Stefan Wild, Mathias Grabau, Miguel Ángel Rivero-Crespo, Antonio Leyva-Pérez, Frank Hauke, Aleksandra Mitrovic, Hans-Peter Steinrück, Katharina Werbach, Michael Fickert, Christian Neiss, Gonzalo Abellán, Thomas Pichler, Vicent Lloret, Andreas Hirsch, and Jose A. Vidal-Moya more...
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Materials science ,010405 organic chemistry ,General Medicine ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences - Abstract
Eine chemisch-reduktive Volumen-Funktionalisierung von dünnlagigem schwarzem Phosphor (BP) gelang unter Verwendung von BP-Interkalationsverbindungen. Durch eine effektive reduktive Aktivierung wurde die kovalente Funktionalisierung des geladenen BP mit Alkylhalogeniden erzielt, wobei eine Öffnung des BP-Gitters und ein höherer Funktionalisierungsgrad als bei neutralen Reaktionsrouten resultieren. more...
- Published
- 2019
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39. Regioirregular and catalytic Mizoroki-Heck reactions
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Mercedes Boronat, Raúl Pérez-Ruiz, Jorge Castellanos-Soriano, Judit Oliver-Meseguer, M. Consuelo Jiménez, Francisco Garnes-Portolés, Juan C. Hernández-Garrido, Miguel López-Haro, Antonio Leyva-Pérez, Rossella Greco, Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España), and Generalitat Valenciana more...
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chemistry.chemical_classification ,Steric effects ,Double bond ,Chemistry ,Process Chemistry and Technology ,Aryl ,Regioselectivity ,chemistry.chemical_element ,Bioengineering ,Biochemistry ,Combinatorial chemistry ,Catalysis ,chemistry.chemical_compound ,QUIMICA ORGANICA ,Intramolecular force ,Cinnamates ,Palladium - Abstract
The palladium-catalysed cross-coupling reaction between alkenes and aryl halides (the Mizoroki–Heck reaction) is a powerful methodology to construct new carbon–carbon bonds. However, the success of this reaction is in part hampered by an extremely marked regioselectivity on the double bond, which dictates that electron-poor alkenes react exclusively on the β-carbon. Here, we show that ligand-free, few-atom palladium clusters in solution catalyse the α-selective intramolecular Mizoroki–Heck coupling of iodoaryl cinnamates, and mechanistic studies support the formation of a sterically encumbered cinnamate–palladium cluster intermediate. Following this rationale, the α-selective intermolecular coupling of aryl iodides with styrenes is also achieved with palladium clusters encapsulated within fine-tuned and sterically restricted zeolite cavities to produce 1,1-bisarylethylenes, which are further engaged with aryl halides by a metal-free photoredox-catalysed coupling. These ligand-free methodologies significantly expand the chemical space of the Mizoroki–Heck coupling. [Figure not available: see fulltext.], This work was supported by MINECO (Spain, projects CTQ 2017-86735-P, PID2019-105391GB-C22 and MAT2017-82288-C2-1-P, Severo Ochoa programme SEV-2016-0683 and the Juan de la Cierva programme). F.G.-P. and R.G. thank ITQ for the concession of a contract. J.O.-M. acknowledges the Juan de la Cierva programme for the concession of a contract, and R.P.-R. and J.C.-S. thank the Plan GenT programme (CIDEGENT/2018/044) funded by Generalitat Valenciana. HR STEM measurements were performed at DME-UCA in Cadiz University, with financial support from FEDER/MINECO (PID2019-110018GA-I00 and PID2019-107578GA-I00). We acknowledge ALBA Synchrotron for allocating beamtime and CLÆSS beamline staff for their technical support during our experiment. more...
- Published
- 2021
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40. Solid–catalyzed esterification reaction of long–chain acids and alcohols in fixed–bed reactors at pilot plant scale
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Aarón Martínez–Castelló, María Tejeda–Serrano, Anna Elzbieta Nowacka, Judit Oliver–Meseguer, Antonio Leyva–Pérez, Ministerio de Ciencia e Innovación (España), Leyva, Antonio, Oliver Meseguer, Judit, Leyva, Antonio [0000-0003-1063-5811], and Oliver Meseguer, Judit [0000-0003-1555-3583] more...
- Subjects
Process Chemistry and Technology ,General Chemical Engineering ,Energy Engineering and Power Technology ,General Chemistry ,Industrial and Manufacturing Engineering - Abstract
The esterification reaction of long–chain acids and alcohols is carried out in both academia and industry with soluble strong acids such as phosphoric or methanesulfonic acid, since the lower diffusion and higher steric hindrance of the long–chain reactants compared to small derivatives (such as methanol or ethanol) severely hampers a smooth esterification on catalytic solids. In order to design an efficient industrial process for the esterification reaction of long–chain acids and alcohols, under flow conditions, solid catalysts are of interest. Here we show that the esterification of different fatty acids with 2–ethyl hexyl alcohol proceeds in very high yields and selectivity when carried out with organic solid acids both in batch and in flow processes, enabling the use of fixed–bed reactors to perform the esterification reaction. To evaluate the process under real industrial conditions, experiments at multi–kilogram scale in pilot plant tubular reactors were carried out, confirming the feasibility of the ton–scale production of long–chain esters over solid catalysts in a continuous process., This work was supported by the MICINN (Spain) (Projects PID2020–115100GB–I00) and J.O.–M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018–036514–I). more...
- Published
- 2022
- Full Text
- View/download PDF
41. Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
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Mercedes Boronat, Antonio Leyva-Pérez, Miguel López-Haro, Rossella Greco, Emilio Pardo, Carlo Marini, Jordi Ballesteros-Soberanas, Juan C. Hernández-Garrido, Donatella Armentano, Jesús Ferrando-Soria, Marta Mon, Judit Oliver-Meseguer, Estefanía Tiburcio, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia, Innovación y Universidades (España) more...
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inorganic chemicals ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,Metal ,Colloid and Surface Chemistry ,Atom economy ,Metal·lúrgia ,Dissolution ,Solvent free ,Chemistry ,Ligand ,Química ,General Chemistry ,Combinatorial chemistry ,0104 chemical sciences ,Soluble/MOF ,Organic reaction ,Alcohols ,visual_art ,visual_art.visual_art_medium ,Palladium - Abstract
Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal-organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation., This work was supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy) and the MINECO (Spain) (Projects PID2019−104778GB−I00, CTQ 2017–86735–P, RTC–2017–6331–5, Severo Ochoa program SEV–2016–0683 and Excellence Unit “Maria de Maeztu” CEX2019−000919−M). E.T. and M.M. thank MINECO and ITQ for the concession of a contract. D.A. acknowledges the financial support of the Fondazione CARIPLO/“Economia Circolare: ricerca per un futuro sostenibile” 2019, Project code: 2019–2090, MOCA and Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities and thanks Dr. Sarah Barnett and David Allan for their assistance at I19 beamline (Proposal No. MT18768-1). Thanks are also extended to the “2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011” (J.F.-S.) and “La Caixa” scholarship (ID 100010434) LCF/BQ/DI19/11730029 (J.B.-S). E.P. acknowledges the financial support of the European Research Council under the European Union’s Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF reactors. J.O.-M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018-036514-I). We gratefully acknowledge to ALBA synchrotron for allocating beamtime and CLÆSS beamline staff for their technical support during our experiment. The computations were performed on the Tirant III cluster of the Servei d’Informàtica of the University of Valencia. more...
- Published
- 2021
42. Zeolites catalyze selective reactions of large organic molecules
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Marta Mon and Antonio Leyva-Pérez
- Published
- 2021
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43. Radical α–alkylation of ketones with unactivated alkenes under catalytic and sustainable industrial conditions
- Author
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Carlos López-Cruz, Avelino Corma, Sergio Sanz-Navarro, Francisco Garnes-Portolés, Antonio Leyva-Pérez, Estela Espinós-Ferri, and Ministerio de Economía y Competitividad (España)
- Subjects
chemistry.chemical_classification ,Steric effects ,010405 organic chemistry ,Process Chemistry and Technology ,Radical ,Salt (chemistry) ,Alkylation ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,chemistry ,Yield (chemistry) ,Organic chemistry ,Reactivity (chemistry) ,Alkyl - Abstract
The industrially–viable aerobic α–alkylation of cyclic and acyclic ketones with allyl and alkyl alkenes in the presence of catalytic amounts of Mn, under homo– and heterogeneous conditions, is achieved here. The substitution of organic peroxides by Mn either as a simple soluble salt or supported in zeolites, in air, generates in–situ peracid radicals and circumvents the aggressiveness of current industrial protocols, to pave the way for the design of sustainable aerobic catalytic systems. Combined reactivity and mechanistic studies show that large cyclic ketones stabilize a radical in the α–position due to a higher polarizability, steric hindrance and no proximity effects. As a proof of concept, the gram–scale synthesis of the industrial fragrance exaltolide is carried out with the Mn catalysts in air, which clearly improves any other previously reported method not only in safety and environmental terms but also in number of synthetic steps and overall yield., ITQ thanks IFF for its continuous support and collaboration. This work was also supported by the MINECO (Spain) (Projects CTQ2017–86735–P and Excellence Unit “Severo Ochoa” SEV–2016–0683). S. S.–N. thanks MINECO the concession of a FPI contract associated to the above CTQ project, and F. G.–P. thanks ITQ for the concession of a contract. more...
- Published
- 2021
44. The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
- Author
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Emilio Pardo, Jesús Ferrando-Soria, Juan Manuel Herrera, Avelino Corma, Antonio Leyva-Pérez, Donatella Armentano, Mercedes Boronat, Jorge Gascon, Francisco R. Fortea-Pérez, Marta Mon, and Dmitrii Osadchii more...
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Chemical process ,Mechanical Engineering ,chemistry.chemical_element ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Heterogeneous catalysis ,01 natural sciences ,Combinatorial chemistry ,0104 chemical sciences ,Catalysis ,chemistry.chemical_compound ,chemistry ,Mechanics of Materials ,Organic chemistry ,General Materials Science ,Metal catalyst ,0210 nano-technology ,Carbene ,Palladium ,Metal clusters - Abstract
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes. more...
- Published
- 2017
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45. Disassembling Metal Nanocrystallites into Sub-nanometric Clusters and Low-faceted Nanoparticles for Multisite Catalytic Reactions
- Author
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Antonio Leyva-Pérez, Rafael Gavara, Irene Domínguez, Judit Oliver-Meseguer, and Avelino Corma
- Subjects
010405 organic chemistry ,Chemistry ,Organic Chemistry ,Inorganic chemistry ,Nanoparticle ,Sonogashira coupling ,010402 general chemistry ,01 natural sciences ,Catalysis ,0104 chemical sciences ,Inorganic Chemistry ,Metal ,Chemical engineering ,visual_art ,visual_art.visual_art_medium ,Physical and Theoretical Chemistry - Published
- 2017
- Full Text
- View/download PDF
46. Intermolecular Carbonyl-olefin Metathesis with Vinyl Ethers Catalyzed by Homogeneous and Solid Acids in Flow
- Author
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Horacio Pérez-Sánchez, José P. Cerón-Carrasco, Antonio Leyva-Pérez, Miguel Ángel Rivero-Crespo, María Tejeda-Serrano, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia, Innovación y Universidades (España) more...
- Subjects
Grob fragmentation ,Heterogeneous catalysis ,010405 organic chemistry ,Chemistry ,Intermolecular force ,General Chemistry ,General Medicine ,010402 general chemistry ,Metathesis ,01 natural sciences ,Carbonyl-olefin metathesis ,Catalysis ,0104 chemical sciences ,In-flow reactions ,Vinyl ethers ,Intramolecular force ,QUIMICA ANALITICA ,Salt metathesis reaction ,Organic chemistry ,Stereoselectivity ,Montmorillonite K10 - Abstract
[EN] The carbonyl-olefin metathesis reaction has experienced significant advances in the last seven years with new catalysts and reaction protocols. However, most of these procedures involve soluble catalysts for intramolecular reactions in batch. Herein, we show that recoverable, inexpensive, easy to handle, non-toxic, and widely available simple solid acids, such as the aluminosilicate montmorillonite, can catalyze the intermolecular carbonyl-olefin metathesis of aromatic ketones and aldehydes with vinyl ethers in-flow, to give alkenes with complete trans stereoselectivity on multi-gram scale and high yields. Experimental and computational data support a mechanism based on a carbocation-induced Grob fragmentation. These results open the way for the industrial implementation of carbonyl-olefin metathesis over solid catalysts in continuous mode, which is still the origin and main application of the parent alkene-alkene cross-metathesis., Financial support by MINECO through the Severo Ochoa program (SEV-2016-0683), Excellence program (CTQ 2017-86735-P, CTQ 2017-87974-R), Retos Col. (RTC-2017-6331-5), and "Convocatoria 2014 de Ayudas Fundacion BBVA a Investigadores y Creadores Culturales" is acknowledged. M.A.R.-C. and M.T.-S. thank ITQ for the concession of a contract. This research was partially supported by the supercomputing infrastructure of Poznan Supercomputing Center. more...
- Published
- 2020
- Full Text
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47. Cyclic metal(oid) clusters control platinum-catalysed hydrosilylation reactions : from soluble to zeolite and MOF catalysts
- Author
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Judit Oliver-Meseguer, Antonio Leyva-Pérez, Emilio Pardo, Piotr Kuśtrowski, José P. Cerón-Carrasco, Klaudia Kapłońska, Miguel Ángel Rivero-Crespo, European Research Council, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia, Innovación y Universidades (España) more...
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Silanes ,010405 organic chemistry ,Chemistry ,Hydrosilylation ,chemistry.chemical_element ,Regioselectivity ,General Chemistry ,Microporous material ,010402 general chemistry ,01 natural sciences ,3. Good health ,0104 chemical sciences ,Catalysis ,Metal ,chemistry.chemical_compound ,visual_art ,visual_art.visual_art_medium ,Organic chemistry ,Platinum ,Zeolite - Abstract
The Pt-catalysed addition of silanes to functional groups such as alkenes, alkynes, carbonyls and alcohols, i.e. the hydrosilylation reaction, is a fundamental transformation in industrial and academic chemistry, often claimed as the most important application of Pt catalysts in solution. However, the exact nature of the Pt active species and its mechanism of action is not well understood yet, particularly regarding regioselectivity. Here, experimental and computational studies together with an ad hoc graphical method show that the hydroaddition of alkynes proceeds through Pt-Si-H clusters of 3-5 atoms (metal(oid) association) in parts per million amounts (ppm), which decrease the energy of the transition state and direct the regioselectivity of the reaction. Based on these findings, new extremely-active (ppm) microporous solid catalysts for the hydrosilylation of alkynes, alkenes and alcohols have been developed, paving the way for more environmentally-benign industrial applications. This journal is, Financial support by MINECO through the Severo Ochoa program (SEV-2016-0683), Excellence program (CTQ 2017-86735-P and CTQ 2017-87974-R) and Retos Col. (RTC-2017-6331-5) is acknowledged. E. P. acknowledges the financial support of the European Research Council under the European Union's Horizon 2020 research and innovation program/ERC Grant Agreement No. 814804, MOF-reactors. M. A. R.-C. thanks ITQ for the concession of a contract and J. O. M. thanks the Juan de la Cierva program for the concession of a contract. We thank V. B. dLL. and N. G. G. for performing degree projects in the ITQ labs. This research was partially supported by the supercomputing infrastructure of Poznan Supercomputing Center. The Electron Microscopy Service of the UPV is also acknowledged. more...
- Published
- 2020
48. Metal-Organic Frameworks as Chemical Nanoreactors: Synthesis and Stabilization of Catalytically Active Metal Species in Confined Spaces
- Author
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Marta Viciano-Chumillas, Emilio Pardo, Avelino Corma, Donatella Armentano, Marta Mon, Jesús Ferrando-Soria, Antonio Leyva-Pérez, European Research Council, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia, Innovación y Universidades (España) more...
- Subjects
Materials science ,010405 organic chemistry ,Química organometàl·lica ,Nanotechnology ,General Medicine ,General Chemistry ,Nanoreactor ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Metal ,Metalls preciosos ,visual_art ,visual_art.visual_art_medium ,Metal-organic framework ,Confined space - Abstract
ConspectusSince the advent of the first metal-organic frameworks (MOFs), we have witnessed an explosion of captivating architectures with exciting physicochemical properties and applications in a wide range of fields. This, in part, can be understood under the light of their rich host-guest chemistry and the possibility to use single-crystal X-ray diffraction (SC-XRD) as a basic characterization tool. Moreover, chemistry on preformed MOFs, applying recent developments in template-directed synthesis and postsynthetic methodologies (PSMs), has shown to be a powerful synthetic tool to (i) tailor MOFs channels of known topology via single-crystal to single-crystal (SC-SC) processes, (ii) impart higher degrees of complexity and heterogeneity within them, and most importantly, (iii) improve their capabilities toward applications with respect to the parent MOFs. However, the unique properties of MOFs have been, somehow, limited and underestimated. This is clearly reflected on the use of MOFs as chemical nanoreactors, which has been barely uncovered. In this Account, we bring together our recent advances on the construction of MOFs with appealing properties to act as chemical nanoreactors and be used to synthesize and stabilize, within their channels, catalytically active species that otherwise could be hardly accessible. First, through two relevant examples, we present the potential of the metalloligand approach to build highly robust and crystalline oxamato- and oxamidato-MOFs with tailored channels, in terms of size, charge and functionality. These are initial requisites to have a playground where we can develop and fully take advantage of singular properties of MOFs as well as visualize/understand the processes that take place within MOFs pores and somehow make structure-functionalities correlations and develop more performant MOFs nanoreactors. Then, we describe how to exploit the unique and singular features that offer each of these MOFs confined space for (i) the incorporation and stabilization of metals salts and complexes, (ii) the in situ stepwise synthesis of subnanometric metal clusters (SNMCs), and (iii) the confined-space self-assembly of supramolecular coordination complexes (SCCs), by means of PSMs and underpinned by SC-XRD. The strategy outlined here has led to unique rewards such as the highly challenging gram-scale preparation of stable and well-defined ligand-free SNMCs, exhibiting outstanding catalytic activities, and the preparation of unique SCCs, different to those assembled in solution, with enhanced stabilities, catalytic activities, recyclabilities, and selectivities. The results presented in this Accounts are just a few recent examples, but highly encouraging, of the large potential way of MOFs acting as chemical nanoreactors. More work is needed to found the boundaries and fully understand the chemistry in the confined space. In this sense, mastering the synthetic chemistry of discrete organic molecules and inorganic complexes has basically changed our way of live. Thus, achieving the same degree of control on extended hybrid networks will open new frontiers of knowledge with unforeseen possibilities. We aim to stimulate the interest of researchers working in broadly different fields to fully unleash the host-guest chemistry in MOFs as chemical nanoreactors with exclusive functional species., This work was supported by the MINECO (Spain) (ProjectsCTQ2016-75671-P, 2017-86735-P, and Excellence Units“Severo Ochoa”and“Maria de Maeztu”SEV-2016-0683 andMDM-2015-0538) and the Ministero dell’Istruzione, dell’Uni-versitàe della Ricerca (Italy). Thanks are also extended to the“2019 Post-Doctoral Junior Leader-Retaining Fellowship, laCaixa Foundation (ID100010434 and Fellowship Code LCF/BQ/PR19/11700011”(J. F.-S.) and the Diamond LightSource for awarded beamtime and provision of synchrotronradiation facility at I19 beamline (D. A.). E.P. acknowledges thefinancial support of the European Research Council underthe European Union’s Horizon 2020 Research and InnovationProgramme/ERC Grant Agreement No. 814804, MOF-reactors. more...
- Published
- 2020
49. Ligand-Free Sub-Nanometer Metal Clusters in Catalysis
- Author
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Judit Oliver–Meseguer and Antonio Leyva–Pérez
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Metal ,Steric effects ,Materials science ,Chemical physics ,Ligand ,visual_art ,Atom ,visual_art.visual_art_medium ,Molecule ,Molecular orbital ,Characterization (materials science) ,Catalysis - Abstract
Recent advances in the synthesis and characterization of ligand-free sub-nanometer metal clusters, either in solution or supported on solids, have enabled their rational use as catalysts in new reactions. These clusters expose all their metal atoms to outer molecules without the potential steric/electronic interferences of ligands, while, at the same time, show defined molecular orbitals to ultimately control the catalytic reaction. Therefore, these clusters somehow combine the advantages of single atom and metal nanoparticles for molecular activation and catalysis. This chapter aims at describing how to prepare, better characterize and apply, on a realistic scale, ligand-free sub-nanometer metal clusters for catalytic processes (many of them of industrial interest) during the last ten years. more...
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- 2020
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50. Nanoceria as a recyclable catalyst/support for the cyanosilylation of ketones and alcohol oxidation in cascade
- Author
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Francisco Garnes-Portolés, Miguel Ángel Rivero-Crespo, Antonio Leyva-Pérez, Ministerio de Economía y Competitividad (España), and Ministerio de Ciencia, Innovación y Universidades (España)
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Cyanosilylation ,010405 organic chemistry ,Aerobic oxidation of alcohols ,010402 general chemistry ,Cyanohydrins ,01 natural sciences ,Recyclable catalyst ,Combinatorial chemistry ,Catalysis ,0104 chemical sciences ,law.invention ,chemistry.chemical_compound ,Nanoceria ,chemistry ,law ,Alcohol oxidation ,QUIMICA ANALITICA ,Organic synthesis ,Calcination ,Lewis acids and bases ,Physical and Theoretical Chemistry ,Bifunctional ,Metal nanoparticles - Abstract
[EN] The cyanosilylation of carbonyl compounds is a fundamental reaction in organic synthesis, to give cyanohydrins. Ketones are particularly reluctant to cyanosilane addition and require the action of a catalyst, and despite many soluble Bronsted and Lewis acids have been employed for this task, it is difficult to find in the open literature catalytic solids able to carry out the reaction. Here, we show that commercially available nanoceria catalyzes the cyanosilylation of different ketones (21 examples) at temperatures between 0 and 50 degrees C, in high yields, under solventless conditions if required. The nanoceria network atoms act in a cooperative way to provide a bifunctional acid-base solid catalyst for the cyanosilylation reaction. The amorphization of nanoceria during reaction, due to acid release, does not hamper the catalytic activity and, indeed, different types of nanoceria, even with supported metal nanoparticles on surface, are active for the reaction, enabling extensive reuses after air calcination and the use of the catalytic material for the aerobic oxidation of alcohols / cyanosilylation reaction. (C) 2020 Elsevier Inc. All rights reserved., Financial support by MINECO (Spain) (Project CTQ 2017-86735P and Excellence Unit "Severo Ochoa"SEV-2016-0683) is acknowledged. F.G.-P. thanks ITQ for a contract and M.A.R-C. thanks Iberdrola Foundation for a fellowship. more...
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- 2020
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