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9 results on '"Juan Sanz García"'

1. Development of a Radical Silylzincation of (Het)Aryl-Substituted Alkynes and Computational Insights into the Origin of the trans-Stereoselectivity

Author

Fabrice Chemla, Karen de la Vega-Hernández, Hélène Gérard, Martin Oestreich, Juan Sanz García, Stéphanie Halbert, Alejandro Perez-Luna, Carolin Fopp, Olivier Jackowski, Frédéric Guégan, Franck Ferreira, Elise Romain, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut für Chemie [TUB Berlin], and Technische Universität Berlin (TU)

Subjects
Vinylsilanes, 010405 organic chemistry, Chemistry, Stereochemistry, Radical reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, chemistry.chemical_element, Silylmetalation, General Chemistry, Zinc, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Stereoselectivity, Silylzinc reagents
Abstract

International audience; Aryl- and hetaryl-substituted acetylenes undergo regio- and stereoselective silylzincation by reaction with [(Me3Si)3Si]2Zn in the presence of Et2Zn (10–110 mol%) as additive. The distinctive feature of this addition across the C−C triple bond is its trans stereoselectivity. The radical nature of the silylzincation process is supported by diagnostic experiments and DFT calculations, which also corroborate the role played by steric effects to obtain that stereoselectivity. The procedure can be combined in one-pot with the copper(I)-mediated electrophilic substitution of the C(sp2)−Zn bond, with retention of the double bond geometry. This makes it valuable for the synthesis of stereodefined di- and trisubstituted vinylsilanes.

Published
2021
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2. Atypical Lone Pair-π Interaction with Quinone Methides in a Series of Imido-Ferrociphenol Anticancer Drug Candidates

Author

Claire Troufflard, Juan Sanz García, Yong Wang, Michael J. McGlinchey, Pascal Pigeon, Gérard Jaouen, Siden Top, Ilaria Ciofini, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chemical Biology (CHEMBIO), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), School of Chemistry and Chemical Biology (UCD), and University College Dublin [Dublin] (UCD)

Subjects
Models, Molecular, Stereochemistry, Supramolecular chemistry, Antineoplastic Agents, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, Crystallography, X-Ray, Imides, 01 natural sciences, Redox, Catalysis, antitumor agents, chemistry.chemical_compound, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Ferrous Compounds, Indolequinones, Imide, Lone pair, quinones, Molecular Structure, 010405 organic chemistry, Drug discovery, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Medicine, General Chemistry, Anticancer drug, 0104 chemical sciences, Quinone, chemistry, non-covalent interactions, Intramolecular force, bioorganometallics, ferrocifen, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract

International audience; Ferrociphenols, especially those possessing a heterocycle at the terminus of an aliphatic chain, display strong anticancer activity via a novel redox mechanism that generates active metabolites such as quinone methides (QMs). X-ray crystallography and UV-Vis spectroscopy reveal that the specific lone pair (lp)-π interaction between a carbonyl group of the imide and the quinone motif of the QM plays an important role in the exceptional cytotoxic behaviour of their imido-ferrociphenol precursors. This intramolecular lp-π interaction markedly enhanced the stability of the QMs and lowered the pKa values of the corresponding phenolates. As the first example of such a non-covalent interaction that stabilizes QMs remotely, it not only expands the scope of the lp-π interaction in supramolecular chemistry, but also represents a new mode of stabilization of a QM. This unprecedented application of lp-π interactions in imido-ferrociphenol anticancer drug candidates may also have great potential in drug discovery and organocatalyst design.

Published
2019
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3. Using Density Based Indexes and Wave Function Methods for the Description of Excited States: Excited State Proton Transfer Reactions as a Test Case

Author

Marco Campetella, Juan Sanz García, Federica Maschietto, Ilaria Ciofini, Chimie ParisTech (ENSCP), Chimie ParisTech, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), Institute of Chemistry for Life and Health Sciences (iCLeHS), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010304 chemical physics, Proton, Chemistry, Charge (physics), Time-dependent density functional theory, 010402 general chemistry, 01 natural sciences, Measure (mathematics), 0104 chemical sciences, Interpretation (model theory), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Intramolecular force, Excited state, 0103 physical sciences, [CHIM]Chemical Sciences, Statistical physics, Physical and Theoretical Chemistry, Wave function, ComputingMilieux_MISCELLANEOUS
Abstract

To provide tools to interpret photochemical reactions, in this paper we demonstrate how a recently developed density-based index (DCT), up to now used in conjunction with time dependent density functional theory methods, can be extended to multiconfigurational methods. This index can guide chemists in the interpretation of photochemical reactions providing a measure of the spatial extent of a photoinduced charge transfer and, more generally, of charge transfer phenomena. This qualitative and quantitative description can be particularly relevant in the case of multiconfigurational calculations providing a simple tool for the interpretation of their complex outputs. To prove the potentiality of this approach we have considered a simple intramolecular excited state proton transfer reaction as study case and applied both wave function (CASSCF-CASPT2) and density-based methods in conjunction with a DCT analysis. Our results confirm that, also in the case of multiconfigurational methods, the DCT provides very u...

Published
2017
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4. Enantiomerization Pathway and Atropochiral Stability of the BINAP Ligand: A Density Functional Theory Study

Author

Martial Boggio-Pasqua, Christine Lepetit, Remi Chauvin, Yves Canac, Juan Sanz García, Photochimie théorique et computationnelle (LCPQ) (PTC), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Atropisomer, Hot Temperature, 010405 organic chemistry, Ligand, Organic Chemistry, Enantioselective synthesis, Stereoisomerism, General Chemistry, Naphthalenes, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Computational chemistry, Thermodynamics, Density functional theory, Chirality (chemistry), Racemization, ComputingMilieux_MISCELLANEOUS, Basis set, BINAP
Abstract

A theoretical study of the enantiomerization pathway of BINAP, the paradigm of atropochiral ligands in asymmetric organometallic catalysis, is reported. Density functional theory was used with the B3PW91 functional and the 6-31G(d,p) basis set. The calculation level was validated through the study of the syn and anti enantiomerization pathways of the 1,1′-binaphthyl reference for which the enantiomerization barrier was calculated to be in good agreement with experimental data. Calculations were then performed on BINAP itself using the same level of theory, and showed that its enantiomerization mechanism follows the syn route through a concerted, yet highly asynchronous, all-chiral process. The enantiomerization barrier was computed at 213 kJ mol(−1) and proved little sensitive to the functional or to the basis set used, with values always larger than 200 kJ mol(−1). The configurational stability of BINAP was finally characterized by a computed Oki’s racemization temperature of 491 °C.

Published
2013
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5. Is photoisomerization required for NO photorelease in ruthenium nitrosyl complexes?

Author

Martial Boggio-Pasqua, Isabelle M. Dixon, Fabienne Alary, Jean-Louis Heully, Juan Sanz García, Photochimie théorique et computationnelle (LCPQ) (PTC), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), 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)-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 du CNRS (INC)-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 de Chimie du CNRS (INC), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3)

Subjects
education.field_of_study, Photoisomerization, 010405 organic chemistry, Organic Chemistry, Population, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, Potential energy, Bond-dissociation energy, Catalysis, 0104 chemical sciences, Computer Science Applications, Ruthenium, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Computational Theory and Mathematics, chemistry, Intramolecular force, Metastability, Physical and Theoretical Chemistry, Triplet state, education
Abstract

The factors that explain the competition between intramolecular NO linkage photoisomerization and NO photorelease in five ruthenium nitrosyl complexes were investigated. By applying DFT-based methods, it was possible to characterize the ground states and lowest triplet potential energy surfaces of these species, and to establish that both photoisomerization and photorelease processes can occur in the lowest triplet state of each species. This work highlights the crucial role of the sideways-bonded isomer, a metastable state also known as the MS2 isomer, in the photochemical loss of NO, while the results obtained also indicate that the population of the triplet state of this isomer is compulsory for both processes and show how photoisomerization and photorelease interfere. Graphical Abstract Illustration of the crucial role of the

Published
2016
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6. Aryne-mediated fluorination: Synthesis of fluorinated biaryls via a sequential desilylation–halide elimination–fluoride addition process

Author

Juan Sanz García, Françoise Colobert, Frédéric R. Leroux, Vincent Diemer, Laboratoire d'innovation moléculaire et applications (LIMA), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nucleophilic addition, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Halide, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, Medicinal chemistry, Silane, Aryne, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Bromide, Furan, Environmental Chemistry, Organic chemistry, Physical and Theoretical Chemistry, Fluoride
Abstract

An unusual aryne-mediated fluorination of aromatic ring systems during the desilylation of ortho -bromo-biphenyl-trimethylsilanes with tetrabutylammonium fluoride (TBAF) is described. In situ formation of an aryne and addition of fluoride affords fluorinated biphenyls. The structures have been undoubtfully confirmed by synthesis of authentic samples via Suzuki–Miyaura cross-coupling and X-ray analysis. In situ trapping experiments with furan proved the transient formation of aryne by fluoride-induced displacement of the TMS group and subsequent bromide elimination.

Published
2012
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7. Establishing the Two-Photon Linkage Isomerization Mechanism in the Nitrosyl Complex trans-[RuCl(NO)(py)4]2+ by DFT and TDDFT

Author

Jean-Louis Heully, Isabelle M. Dixon, Martial Boggio-Pasqua, Isabelle Malfant, Juan Sanz García, Fabienne Alary, Photochimie théorique et computationnelle (LCPQ) (PTC), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Photoisomerization, 010405 organic chemistry, Chemistry, Time-dependent density functional theory, 010402 general chemistry, 01 natural sciences, Potential energy, Reversible reaction, 0104 chemical sciences, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Nuclear magnetic resonance, Chemical physics, Metastability, Density functional theory, Singlet state, Physical and Theoretical Chemistry, Isomerization, ComputingMilieux_MISCELLANEOUS
Abstract

The density functional theory calculations presented in this work allow the first rationalization of the full linkage photoisomerization mechanism of trans-[RuCl(NO)(py)4](2+), in both the forward and reverse directions. These mechanisms are consistent with the experimental data establishing that blue-light irradiation triggers the forward process, while red or IR photons trigger the reverse process. Characterization of the singlet and lowest triplet potential energy surfaces shows that, despite the unfavorable thermodynamic character of the forward process, the topologies of the surfaces and particularly some crucial surface crossings enable the isomerization. In the forward Ru-NO → Ru-ON direction, a sequential two-photon absorption mechanism is unraveled that involves a sideways-bonded metastable state. In contrast, in the reverse reaction, two mechanisms are proposed involving either one or two photons.

Published
2015
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8. Computational analysis of the nature and strength of the supramolecular contacts involved in the binding of chloride anions by imidazolium-based cyclic receptors

Author

Laura Rodríguez, Juan Sanz García, Patrick Gamez, and Arturo Robertazzi

Subjects
Anions, Binding Sites, Macrocyclic Compounds, Chemistry, Stereochemistry, Hydrogen bond, Supramolecular chemistry, Imidazoles, Aromaticity, Receptors, Artificial, Crystallography, X-Ray, Chloride, Ion, Crystallography, Chlorides, medicine, Molecule, Density functional theory, Computer Simulation, Physical and Theoretical Chemistry, Receptor, medicine.drug
Abstract

The supramolecular bonding contacts driving the recognition of chloride ions by macrocyclic imidazolium-based receptors have been investigated by density functional theory calculations, both in vacuo and in solution (DMSO). This computational study reveals that the most stable host-guest complexes in vacuo and solution are different. While the anion interacts by means of two C-H···Cl(-) hydrogen bonds with the host molecule in vacuo (in a similar manner to that observed in the published single-crystal X-ray structure of the Cl-host complex), four C-H···Cl(-) contacts are clearly present in solution, as observed experimentally by earlier studies. In addition, the computed optimal Cl-host complex in solution confirms that the cavity of the host macrocycle, formed by four aromatic rings, does not includes the anions, which are located outside the cyclic receptor with which they interact through two CPh-H···Cl(-) hydrogen bonds and two unconventional (CIm-H)(+)···X(-) interactions.

Published
2012

9. ChemInform Abstract: Aryne-Mediated Fluorination: Synthesis of Fluorinated Biaryls via a Sequential Desilylation-Halide Elimination-Fluoride Addition Process

Author

Françoise Colobert, Juan Sanz García, Vincent Diemer, and Frédéric R. Leroux

Subjects
chemistry.chemical_compound, chemistry, Bromide, Furan, Halide, Halogenation, General Medicine, Fluoride addition, Ring (chemistry), Fluoride, Medicinal chemistry, Aryne
Abstract

An unusual aryne-mediated fluorination of aromatic ring systems during the desilylation of ortho -bromo-biphenyl-trimethylsilanes with tetrabutylammonium fluoride (TBAF) is described. In situ formation of an aryne and addition of fluoride affords fluorinated biphenyls. The structures have been undoubtfully confirmed by synthesis of authentic samples via Suzuki–Miyaura cross-coupling and X-ray analysis. In situ trapping experiments with furan proved the transient formation of aryne by fluoride-induced displacement of the TMS group and subsequent bromide elimination.

Published
2012
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