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9,997 results on '"[CHIM.ORGA]Chemical Sciences/Organic chemistry"'

1. Very intense polarized emission in self-assembled room temperature metallomesogens based on Zn(<scp>ii</scp>) coordination complexes: an experimental and computational study

Author

Elisabeta I. Szerb, Emilie Voirin, Otilia Costisor, Bertrand Donnio, Mario Amati, Benoît Heinrich, Massimo La Deda, Valentin Badea, Angela Candreva, Giuseppe Di Maio, Evelyn Popa, Adelina A. Andelescu, Donnio, Bertrand, Università della Calabria [Arcavacata di Rende] (Unical), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Romanian Academy, Politehnica University of Timisoara (UPT), and Università degli studi della Basilicata [Potenza] (UNIBAS)

Subjects
[CHIM.INOR] Chemical Sciences/Inorganic chemistry, [PHYS.PHYS.PHYS-OPTICS] Physics [physics]/Physics [physics]/Optics [physics.optics], [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Quenching (fluorescence), Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Transition dipole moment, Quantum yield, Mesophase, General Chemistry, Time-dependent density functional theory, [CHIM.COOR] Chemical Sciences/Coordination chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Crystallography, chemistry.chemical_compound, chemistry, Excited state, [CHIM.CRIS]Chemical Sciences/Cristallography, Materials Chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [CHIM.CRIS] Chemical Sciences/Cristallography, Terpyridine
Abstract

International audience; Three room-temperature metallomesogens based on Zn(II) cations pentacoordinated by different chelating N^N^N terpyridines and two monodentate gallate co-ligands were designed and synthesized. Depending on the terpyridine ligand's tip functionality, the complexes self-assemble into either a 3D hexagonal mesophase or into a columnar hexagonal mesophase. A systematic study between the structure (molecular architecture, arrangement of the molecules and columns, and chains in both types of mesophases) and photophysical properties (emission maxima and yields, lifetimes of the excited states in the mesophase), correlated with investigations of single molecules in solution, was conducted. Remarkably, one complex exhibited a record quantum yield of 95.0% in solution, while in the mesophase, despite quenching due to the radiative deactivation from the ILCT state, still retained a considerable emission yield of ϕ = 20.2%. The polarized emission of an oriented film, determined for the first time in columnar metallomesogens, shows a dichroic emission ratio (I||/I⊥) of 1.30. DFT and TDDFT computational studies confirmed the origin of the observed fluorescence anisotropy from the transition dipole moment oriented along the C2 symmetry axis of the molecule combined with a high level of order in the 3D mesophase.

Published
2022

2. Synthesis of Heterospirocycles through Gold‐(I) Catalysis: Useful Building Blocks for Medicinal Chemistry

Author

Kossi Efouako Soklou, Hamid Marzag, Karen Plé, Sylvain Routier, Béatrice Vallée, Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PLE, Karen, Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nitrogen heterocycles, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Molecular Diversity, Gold catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Synthetic methods, Organic chemistry, Spiro Compounds
Abstract

International audience; Gold-(I) catalysis was used for the intramolecular cyclization of tertiary alcohols with terminal alkynes to form diverse aza-spirocycles. The reaction was carried out with low catalyst loading under microwave irradiation to give both sulfonylated and acylated spirocyclic nitrogen derivatives. Gram scale spirocyclization was carried out and demonstrates the robustness of the reaction. An intramolecular Mizoroki-Heck reaction was performed to give several tetracyclic spirocycles. Double bond reduction and selective protecting group manipulation gave spiropiperazine and spiromorpholine derivatives. These compounds were incorporated into biologically relevant scaffolds to give the first selective spirocyclic inhibitors of LIMK.

Published
2021

3. Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Author

Andrei Golushko, Florent Noël, Shaofei Zhang, Marie Vayer, Nazanin Rezajooei, Christopher N. Rowley, Vuk D. Vuković, Joseph Moran, David Lebœuf, Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Department of Chemistry, Memorial University of Newfoundland, St. John's, Canada, Memorial University of Newfoundland [St. John's], Carleton University, univOAK, Archive ouverte, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemical Engineering, Biochemistry (medical), [CHIM.CATA] Chemical Sciences/Catalysis, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Alkylation, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Electrophile, Materials Chemistry, Nucleophilic substitution, Environmental Chemistry, Organic chemistry, SN2 reaction, Brønsted–Lowry acid–base theory, Friedel–Crafts reaction
Abstract

International audience; Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they are widely available, require no pre-activation, and produce no stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal epoxides are compatible with existing intermolecular Friedel-Crafts methodologies, and sequential Friedel-Crafts reactions starting from epoxides consequently remain underexplored. Here, we report that these limitations are easily overcome using Brønsted acid catalysis in hexafluoroisopropanol (HFIP) as a solvent. Electron-poor aromatic epoxides and aliphatic epoxides undergo stereospecific arylation to give an alcohol which, depending on the reaction conditions, can partake in a second nucleophilic substitution with a different arene in one pot. Phenyl ethanols react through a phenonium intermediate, whereas simple aliphatic alcohols participate in a rare intermolecular SN2 Friedel-Crafts process, delivering linear products exclusively. This work provides an alternative to metal-catalyzed cross-couplings for accessing important scaffolds, widening the range of applications of the Friedel-Crafts reaction

Published
2021

4. Synthesis of cyclodextrins-metronidazole inclusion complexes and incorporation of metronidazole - 2-hydroxypropyl-β-cyclodextrin inclusion complex in chitosan nanoparticles

Author

Sandrine Rup-Jacques, Fouzia Belaib, Sarra Bensouiki, Assia Ikhlef, Abdeslam-Hassen Meniai, Pierre Magri, Michèle Sindt, Laboratory of Environmental Process Engineering, (LEPE), Laboratory of Reaction Engineering, Faculty of Mechanical Engineering and Process Engineering, USTHB, BP 32, 16111, Algiers, Algeria, Laboratoire du médicament et développement durable, Faculty of Process Engineering, Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes (LCP-A2MC), Université de Lorraine (UL), Biotechnology Research Center, and Laboratory of Environmental Process Engineering

Subjects
Scanning electron microscope, 02 engineering and technology, Analytical Chemistry, Inorganic Chemistry, Chitosan, 03 medical and health sciences, chemistry.chemical_compound, Dynamic light scattering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Thermal stability, Fourier transform infrared spectroscopy, Solubility, Spectroscopy, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, technology, industry, and agriculture, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Controlled release, chemistry, 0210 nano-technology, Nuclear chemistry
Abstract

Inclusion complexes (ICs) of metronidazole (MTZ) with β-cyclodextrin (BCD) and its derivative 2-hydroxypropyl-β-cyclodextrin (HPBCD) were prepared to improve its apparent solubility. A 1:1 stoichiometry has been proposed for both ICs according to the Job's plots. The estimation of association constants and thermodynamic parameters demonstrated that the incorporation of MTZ in both cavities of cyclodextrins (CDs) is a spontaneous exothermic process. Nuclear magnetic resonance spectroscopy (NMR), two-dimensional (2D) NMR, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) investigations were used to ascertain the structure of ICs and that prove their formation. Thermal analysis showed that the thermal stability of MTZ was improved in the presence of both CDs. The in vitro drug release of ICs showed a considerable increase in the dissolution rate in comparison with the pure MTZ. An improvement of antibacterial activity was observed after encapsulation, especially for MTZ-HPBCD IC. Then chitosan (CS) nanoparticles (NPs) were prepared from the preformed MTZ-HPBCD IC by ionic gelation method. FTIR confirmed that MTZ-HPBCD IC has successfully entrapped in CS NPs. Transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM) images and dynamic light scattering (DLS) show that the NPs have a spherical shape with a uniform diameter. The in vitro release profile of NPs showed a controlled-release of MTZ suggesting that such MTZ-HPBCD IC-loaded CS NPs can be an efficient alternative to modify the MTZ release and increase its solubility.

Published
2022

5. Study of the reactivity of 1,1’-dimethylbistetrazole towards catalytic hydrogenation and chemical reduction

Author

Teddy Gilloux, Guy Jacob, Chaza Darwich, Henri Delalu, Emilie Labarthe, Laboratoire Hydrazines et Composés Energetiques Polyazotés (LHCEP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-HERAKLES - SAFRAN-Centre National d'Études Spatiales [Toulouse] (CNES)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ArianeGroup, Direction des lanceurs, and Centre National d'Études Spatiales [Toulouse] (CNES)

Subjects
1 1'-dimethylbistetrazole, Reaction mechanism, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Atmospheric temperature range, 010402 general chemistry, Retro-[3 + 2]-cycloaddition, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Chemical reduction, Catalytic hydrogenation, Tetrazole, Reactivity (chemistry), Physical and Theoretical Chemistry, Lithium aluminum hydride, Derivative (chemistry)
Abstract

International audience; Investigating the possibility of a straightforward formation of tetrazoline or tetrazolidine structures, the reactivity of a tetrazole derivative towards reducing conditions has been studied. The catalytic hydrogenation of 1,1’-dimethylbistetrazole (DMBT) was carried out using various catalysts (Pd/C, Pt/C, Rh/C, Pd/Pt/C, Lindlar, PtO2 and Raney Ni) over a wide range of hydrogen pressure (35–150 bar) and a temperature range from 20 to 60 °C. This exhaustive study enabled to find the optimal conditions for DMBT hydrogenation and to suggest a plausible reaction mechanism. The chemical reduction of DMBT was conducted using several hydrides (BH3, NaBH4, DIBAL and LiAlH4). The reduction products were identified subsequently to conditions optimizing. The suggested reaction mechanism, featuring a retro-[3 + 2]-cycloaddition, was validated by both experimental and theoretical approaches.

Published
2021

6. Crystallization-Induced Diastereomer Transformation of α-Bromo α′-Sulfinyl Ketones. Diastereodivergent Synthesis of (+)-α-Conhydrine and (−)-β-Conhydrine

Author

Erwann Grenet, Pierre-Yves Geant, Xavier J. Salom-Roig, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Conhydrine, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Alkaloid, Organic Chemistry, Diastereomer, 010402 general chemistry, 01 natural sciences, Biochemistry, Carbonyl group, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Transformation (genetics), Enantiopure drug, chemistry, law, Physical and Theoretical Chemistry, Crystallization, ComputingMilieux_MISCELLANEOUS
Abstract

Crystallization-Induced Diastereomer Transformation (CIDT) of α-bromo-α'-(R)-sulfinylketones is reported. This process provides not readily accessible enantiopure stereolabile α-bromoketones, which after diastereoselective carbonyl group reduction lead to the corresponding highly value-added anti and syn-bromohydrins with excellent diastereoselectivities. As an application, a diastereodivergent synthesis of enantiopure hemlock alkaloid (+)-α-conhydrine and its diastereomer (-)-β-conhydrine is also described.

Published
2021

7. Synthesis of Cyclopentenones with C4-Quaternary Stereocenters via Stereospecific [3,3]-Sigmatropic Rearrangement and Applications in Total Synthesis of Sesquiterpenoids

Author

Weiping Zhou, Arnaud Voituriez, Institut de Chimie des Substances Naturelles (ICSN), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Sulfonium, Stereochemistry, Cationic polymerization, Total synthesis, General Chemistry, Sigmatropic reaction, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Stereocenter, chemistry.chemical_compound, Colloid and Surface Chemistry, Stereospecificity, chemistry, Propargyl, Enantiomer
Abstract

International audience; A cationic gold(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium leads after cyclization to cyclopentenones with a C4-quaternary stereocenter. Starting with simple vinyl sulfoxides and propargyl silane, numerous compounds were isolated with moderate to good yields and excellent enantiomeric excesses (26 examples). The application of this simple methodology allowed the efficient total synthesis of five natural sesquiterpenoids, including enokipodin A and B, hitoyopodin A, lagopodin A and the isocuparene-3,4-diol.

Published
2021

8. Impact of the Difluoromethylene Group in the Organocatalyzed Acylative Kinetic Resolution of α,α‐Difluorohydrins

Author

Adrien Quintard, Daniela Andrei, Jean-Marc Pons, Jérémy Merad, Maurice Médebielle, Cyril Bressy, Titouan Desrues, Jean-Luc Parrain, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), ANR-18-CE07-0036,AMPLI,Amplification d'Enantiosélectivité en Organocatalyse: Criblage Rapide de Catalyseurs, Développements & Applications Synthétiques(2018), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Enantioselective, Kinetic Resolution, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organcatalysis, Enantioselective synthesis, chemistry.chemical_element, Context (language use), General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Adduct, Kinetic resolution, Acylation, chemistry, Alcohols, fluorine, Organocatalysis, Fluorine, Moiety
Abstract

International audience; Due to the omnipresence of chiral organofluorine compounds in pharmaceutical, agrochemical, and material chemistry, the development of enantioselective methods for their preparation is highly desirable. In the present study, the enantioselective organocatalyzed acylation of a,a-difluorohydrins using a commercially available chiral isothiourea is reported through a kinetic resolution (KR) process. It reveals that the difluoromethylene moiety (C(sp 3)F 2) can serve as a directing group through electrostatic fluorine-cation interactions, greatly improving the enantioselectivity of the KR. In this context, a broad range of fluorinated alcohols such as valuable 4,4-difluoro-1,3-diols could be synthesized with exquisite enantiocontrol (typically > 99:1 er). Turning to 2,2difluoro-1,3-diols, we also demonstrated that aromatic and fluorinated groups were mutually compatible to provide the expected enantioenriched adducts with > 99:1 er.

Published
2021

9. Versatile Access to Tetrasubstituted 2-Amidoacroleins through Formal Silylformylation of Ynamides

Author

Morgan Donnard, Stéphane Golling, Frédéric R. Leroux, 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
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Isocyanide, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, Rapid access, Physical and Theoretical Chemistry
Abstract

International audience; In this paper we are reporting the first regio-and stereo-selective silylformylation of ynamides. This reaction is tolerant to a wide range of functional groups around the ynamides. The substitution of CO by an isocyanide makes this reaction safer and more practical than standard silylformylation reactions. It overall represents a versatile and rapid access to various tetrasubstituted 3-silyl-2-amidoacrolein derivatives. The synthetic potential of these new building blocks has been evaluated by performing several post-functionalization.

Published
2021

10. Precise Rate Control of Pseudorotaxane Dethreading by pH-Responsive Selectively Functionalized Cyclodextrins

Author

Matthieu Sollogoub, Sawsen Cherraben, Guillaume Vives, Jérémy Scelle, Bernold Hasenknopf, 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), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Substitution (logic), Rate control, Stimulus (physiology), 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Threading (manufacturing), Physical and Theoretical Chemistry
Abstract

International audience; A family of cyclodextrins functionalized with zero, one, two, or six amines was shown to control the rate of their threading and dethreading on a molecular axle depending on the pH and their substitution pattern. The originality of this system lies in the rate control of the switch by operating the stimulus directly on the macrocycle.

Published
2021

11. Subsurface‐Carbon‐Induced Local Charge of Copper for an On‐Surface Displacement Reaction

Author

Ye Sun, Flemming Besenbacher, Cristina Mattioli, Wenlong E, Shaoshan Wang, Miao Yu, Lev Kantorovich, André Gourdon, Xueming Yang, Pengcheng Ding, Zhuo Li, Groupe NanoSciences (CEMES-GNS), Centre d'élaboration de matériaux et d'études structurales (CEMES), 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 de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-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), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Harbin Institute of Technology (HIT), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences [Changchun Branch] (CAS), Center for Condensed Matter Science and Technology, Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Department of Physics, King's College London, Interdisciplinary Nanoscience Center (iNANO), and Aarhus University [Aarhus]

Subjects
Materials science, Proton, FOS: Physical sciences, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, Carbide, Deprotonation, Physics - Chemical Physics, Atom, displacement reaction, on-surface synthesis, Single displacement reaction, Chemical Physics (physics.chem-ph), catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemistry, Copper, displacement reactions, 0104 chemical sciences, Condensed Matter - Other Condensed Matter, Carbon doping, local charge, chemistry, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Carbon, Other Condensed Matter (cond-mat.other), carbon doping
Abstract

Transition metal carbides have sparked unprecedented enthusiasm as high-performance catalysts in recent years. Still, the catalytic properties of copper (Cu) carbide remain unexplored. By introducing subsurface carbon (C) to Cu(111), displacement reaction of proton in carboxyl acid group with single Cu atom is demonstrated at the atomic scale and room temperature. Its occurrence is attributed to the C-doping induced local charge of surface Cu atoms (up to +0.30 e/atom), which accelerates the rate of on-surface deprotonation via reduction of the corresponding energy barrier, thus enabling the instant displacement of a proton with a Cu atom when the molecules land on the surface. Such well-defined and robust Cu$^{\delta +}$ surface based on the subsurface C doping offers a novel catalytic platform for on-surface synthesis., Comment: Angewandte Chemie International Edition, Wiley-VCH Verlag, 2021

Published
2021

12. Substituent Effects in 3,3’ Bipyrazole Derivatives. X-ray Crystal Structures, Molecular Properties and DFT Analysis

Author

Tarik Harit, Fouad Malek, Driss Eddike, Monique Tillard, Mahmoud Rahal, Ibrahim Bouabdallah, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Substituent, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Crystal structure, Triclinic crystal system, substituent, 010402 general chemistry, DFT, 01 natural sciences, reactivity indices, chemistry.chemical_compound, Tetragonal crystal system, [CHIM.CRIS]Chemical Sciences/Cristallography, Molecule, QD1-999, General Environmental Science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, bipyrazole, 0104 chemical sciences, Chemistry, Crystallography, Molecular geometry, chemistry, General Earth and Planetary Sciences, Density functional theory, Single crystal
Abstract

International audience; The single crystal X-ray structure of new 1,1’-bis(2-nitrophenyl)-5,5’-diisopropyl-3,3’-bipyrazole, 1, is triclinic P I–, a = 7.7113(8), b = 12.3926(14), c = 12.9886(12) Å, α = 92.008(8), β = 102.251(8), γ = 99.655(9)°. The structural arrangement is compared to that of 5,5’-diisopropyl-3,3’-bipyrazole, 5, whose single crystal structure is found tetragonal I41/a, a = b = 11.684(1), c = 19.158(1) Å. The comparison is also extended to the structures previously determined for 1,1’-bis(2-nitrophenyl)-5,5’-propyl-3,3’-bipyrazole, 2, 1,1’-bis(4-nitrophenyl)-5,5’-diisopropyl-3,3’-bipyrazole, 3, and 1,1’-bis(benzyl)-5,5’-diisopropyl-3,3’-bipyrazole, 4. Density Functional Theory (DFT) calculations are used to investigate the molecular geometries and to determine the global reactivity parameters. The geometry of isolated molecules and the molecular arrangements in the solid state are analyzed according to the nature of the groups connected to the bipyrazole core.

Published
2021

13. Detection of Isotopic Atropisomerism Based on ortho-H/D Discrimination

Author

Kazuya Saito, Christian Roussel, Osamu Kitagawa, Yuuki Fujimoto, Shota Miwa, Asumi Iida, Elsa Caytan, Shibaura Institute of Technology, Tokyo University of Pharmacy and Life Sciences (TUPLS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was partially supported by JSPS KAKENHI (C 20K06945)., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Atropisomer, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Diastereomer, Optically active, 010402 general chemistry, 01 natural sciences, Biochemistry, Spectral line, 0104 chemical sciences, 3. Good health, Crystallography, Asymmetric carbon, Axial chirality, Physical and Theoretical Chemistry
Abstract

International audience; Racemic and optically active 3-(2-deuteriophenyl)-2-(1-phenylpropan-2-yl)quinazoline-4-thiones were prepared. The nuclear magnetic resonance spectra clearly show that they exist as a 1:1 mixture of diastereomers due to the isotopic atropisomerism based on ortho-H/D discrimination (N-C axial chirality) and a chiral carbon.

Published
2021

14. Manganese‐Catalyzed Cross‐Coupling Processes

Author

Marc Taillefer, Florian Jaroschik, Xiaoping Liu, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
education, Stille coupling, mechanism, chemistry.chemical_element, Homogeneous catalysis, Manganese, 010402 general chemistry, C-C bond formation, 01 natural sciences, Catalysis, Kumada coupling, cross-coupling, arylation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, homogeneous catalysis, 0104 chemical sciences, Stille reaction, Coupling (electronics), biaryls, chemistry, C-heteroatom bond formation, Chemical physics, manganese, trace metal contamination
Abstract

International audience; This chapter describes recent developments in the manganese-catalyzed crosscoupling reactions for the formation of CC or C-heteroatom bonds, including C-N, CO , C-S and C-B bonds. The nature of the organic halide and the organometallic coupling partner (organolithium, Grignard or organostannyl reagents) are important parameters in these reactions. Mechanistic studies are discussed as well as the recently arisen question about the influence of trace-metal contamination in certain reactions.

Published
2021

15. Critical Ligand and Salt Effects in Organomagnesiate‐Promoted 3,3‐Disubstituted Phthalides Synthesis from 2‐Iodobenzoate Derivatives

Author

Philippe C. Gros, Charles T. O'Hara, Sabrina Touchet, Callum Yeardley, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), and University of Strathclyde [Glasgow]

Subjects
chemistry.chemical_classification, Ketone, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, Biological activity, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Yield (chemistry), Intramolecular force, Halogen, QD, Reactivity (chemistry), Physical and Theoretical Chemistry, Bimetallic strip
Abstract

International audience; Phthalides, also called isobenzofuranones, are widespread in many biologically active compounds and natural products. To date, most of their synthetic routes are non-convergent. Herein we report a convergent route using a metal halogen exchange (MHE) strategy. Indeed MHE of easily available 2-iodobenzoate derivatives, using the bimetallic organomagnesiate complex (rac)-(BIPHEN)BuMgLi, where (rac)-BIPHEN is (rac)-5,5′,6,6′-tetramethyl-3,3′-di-t-butyl-1,1′-biphenyl-2,2′-diol, followed by addition of a ketone which lead to an intramolecular cyclisation, and the formation of a series of diverse 3,3-disubstituted isobenzofuranones in good yield. Among the several MHE agents investigated, (rac)-(BIPHEN)BuMgLi was the only one to make such a process possible with full tolerance of various reactive functional substituents useful for subsequent transformations. The synthetic pathway to access the magnesiate has been found to play a prominent role in its reactivity. Therefore, the bimetallic magnesiate complex has been characterized by solution-state 1H, 7Li and 1H DOSY NMR experiments.

Published
2021

16. Valmet Chiral Schiff‐Base Ligands And Their Copper(II) Complexes as Organo, Homogeneous and Heterogeneous Catalysts for Henry, Cyanosilylation and Aldol Coupling Reactions

Author

Zinnia Arora, Bogdan Cojocaru, Pascal Granger, Vasile I. Pârvulescu, Diana-Ioana Eftemie, Catalin Maxim, Anamaria Hanganu, Marius Andruh, Adela Spinciu, Octavian Dumitru Pavel, Madalina Tudorache, CNRS, Centrale Lille, ENSCL, Univ. Artois, Université de Lille, Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181, University of Bucharest (UniBuc), Romanian Academy, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Ministry of Research, Innovation and Digitization, CNCS/CCCDI – UEFISCDI, project numbersPN-III-P1-1.2-PCCDI-2017-0541 1/2018, PN-III-P4-ID-PCCF-2016-0088 17/2021, PN-III-P4-ID-PCE-2020-1532, PNCDI III, European Project: 860322,H2020-EU.1.3.1.,H2020-MSCA-ITN-2019,CCIMC(2020), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cyanosilylation, L- and D-valmet ligands, Nitroaldol reaction, chemistry.chemical_element, Cu-complex, 010402 general chemistry, 01 natural sciences, Catalysis, Coupling reaction, Inorganic Chemistry, Benzaldehyde, Immobilization, chemistry.chemical_compound, Aldol reaction, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Schiff base, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Ligand, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Copper, 0104 chemical sciences, chemistry, Henry reaction
Abstract

International audience; Cyanosilylation, aldol coupling and asymmetric Henry reactions were carried out with L- and D-valmet ligands in different configurations: i) coordinated to sodium ions, as organocatalysts, with week base properties, ii) complexes with copper(II), as homogeneous catalysts, and iii) immobilized copper(II) complexes onto graphene oxide (GO) as heterogeneous catalysts. For the reaction of benzaldehyde and nitromethane in water these afforded an asymmetric Henry reaction, with a spectacular increase of the conversion and ee (92.5 and 95.8 %, respectively) after the deposition on GO. Ligand complexed copper was also effective for cyanosilylation and Aldol coupling reaction.

Published
2021

17. Photoactivatable Small‐Molecule Inhibitors for Light‐Controlled TAM Kinase Activity

Author

Sandrine Piguel, Liliane Mouawad, Sophie Bombard, Thomas Boddaert, Julie Le Bescont, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and bombard, sophie

Subjects
protein kinases, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Hardware_PERFORMANCEANDRELIABILITY, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, small molecule inhibitors, 01 natural sciences, Small molecule, imidazopyridines, 0104 chemical sciences, 3. Good health, Analytical Chemistry, Biochemistry, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Hardware_INTEGRATEDCIRCUITS, photopharmacology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, photocaging, Physical and Theoretical Chemistry, Kinase activity
Abstract

International audience; Supporting information for this article is given via a link at the end of the document.

Published
2021

18. Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP‐enhanced 15 N and 13 C Solid‐State NMR

Author

Arnaud Huguet, Vytautas Klimavicius, Gerd Buntkowsky, Christelle Anquetil, Frédérique Pourpoint, Olivier Lafon, Torsten Gutmann, Sylvie Derenne, Hiroki Nagashima, Florian Venel, Andrew G. M. Rankin, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Milieux Environnementaux, Transferts et Interactions dans les hydrosystèmes et les Sols (METIS), École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Technische Universität Darmstadt (TU Darmstadt), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), École Pratique des Hautes Études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Technische Universität Darmstadt - Technical University of Darmstadt (TU Darmstadt)

Subjects
geography, geography.geographical_feature_category, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Analytical chemistry, chemistry.chemical_element, Estuary, Nuclear magnetic resonance spectroscopy, Carbon-13 NMR, 010402 general chemistry, 01 natural sciences, Nitrogen, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Salinity, chemistry.chemical_compound, Solid-state nuclear magnetic resonance, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, 13. Climate action, Amide, Dissolved organic carbon, 14. Life underwater, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of 13 C NMR spectra and generally precludes the observation of 15 N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of 13 C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced 13 C NMR spectra indicate that the 13 C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of 15 N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.

Published
2021

19. Auto Tandem Catalysis: Asymmetric Vinylogous Cycloaddition/Kinetic Resolution Sequence for the Enantioselective Synthesis of Spiro‐Dihydropyranone from Benzylidene Meldrum's Acid

Author

Régis Guillot, Giang Vo-Thanh, Jean-François Brière, Chloée Bournaud, Martial Toffano, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tandem, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Enantioselective synthesis, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, Meldrum's acid, 01 natural sciences, Cycloaddition, 0104 chemical sciences, Kinetic resolution, Catalysis, chemistry.chemical_compound, chemistry, Organocatalysis, Sequence (medicine)
Abstract

International audience; A catalytic enantioselective vinylogous domino reaction has been achieved from ketone-derived benzylidene Meldrum's acid and α-ketolactones to provide spirolactone dihydropyranones with more than 99% ee. An Auto Tandem Catalysis (ATC) process resulting from dual and complementary role of (DHQ)2PHAL organocatalyst resulted in a sequence involving an asymmetric vinylogous formal (4+2) cycloaddition of benzylidene and the subsequent kinetic resolution operating through a 1,3-prototropic shift leading to good yields (>50%) and the high selectivity.

Published
2021

20. Construction of Enantioenriched 4,5,6,7‐Tetrahydrofuro[2,3‐ b ]pyridines through a Multicatalytic Sequence Merging Gold and Amine Catalysis

Author

Abdelilah Takfaoui, Manon Genet, Christine Greck, Jérôme Marrot, Xavier Moreau, Institut Lavoisier de Versailles (ILV), and Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aza-Diels-Alder, Aminocatalysis, Saturated heterocycles, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Gold catalysis, Sequence (biology), [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Cycloaddition, Relay catalysis, 0104 chemical sciences, Catalysis, Cycloisomerization, Diphenylprolinol silyl ether, Aza-Diels–Alder reaction, Stereoselectivity, Amine gas treating
Abstract

International audience; A series of enantioenriched 4,5,6,7-tetrahydrofuro[2,3-b]pyridines were accessed by a cycloisomerization/cycloaddition strategy. Starting from ynamide derivatives and aldehydes, yields ranging from 27 to 90% and high levels of stereoselectivity (de>95%, 93–99% ee) were obtained through sequential relay catalysis. The concurrent use of a gold complex with a diphenylprolinol silyl ether was applied to a combination of diversely functionalized substrates.

Published
2021

21. Hemisyntheses and In-silico Study of New Analogues of Carlina Oxide from Carthamus Caeruleus Roots

Author

Joëlle Pérard, Mohammed El Amine Dib, Zoheir Arrar, Imane Rihab Mami, Tabet Zatla Amina, Université de Tlemcen, Cibles Thérapeutiques et conception de médicaments (CiTCoM - UMR 8038), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)

Subjects
In silico, Carthamus, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Plant Roots, reductive amination, Molecular Docking Simulation, Enterococcus faecalis, law.invention, Steam distillation, 03 medical and health sciences, 0302 clinical medicine, Column chromatography, law, Carlina oxide, Drug Discovery, Furans, Vilsmeier-Haack reaction, Essential oil, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, Molecular Structure, biology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Medicine, DNA gyrase inhibitors, biology.organism_classification, Combinatorial chemistry, Computer Science Applications, Enzyme, chemistry, 13. Climate action, Docking (molecular), Alkynes, 030220 oncology & carcinogenesis, Molecular docking, Software
Abstract

Aim and Objective: Nowadays, developing effective antibiotics for bacteria control has become difficult due to increased resistance to the available medicines in the market. Essential oils have very interesting biological properties; some of their components have very powerful antiviral and antibacterial properties. Carthamus caeruleus is a plant that has antibacterial and antioxidant activity due to the presence of an acetylenic compound, Carlina oxide. The aim of this work was to provide for the first time the chemical modifications to the structure of Carlina oxide and the in-silico study of these analogues. Materials and Methods: The essential oil of Carthamus caeruleus was extracted by steam distillation in a Clevenger-type apparatus. Carlina oxide component was separated by column chromatography. Five new analogues were synthetized and identified by spectroscopic analyses (RMN, IR and SM). Molecular docking simulation study was performed using Molecular Operating Environment software (MOE) on three enzymes of bacterial origin (Streptococcus pyogenesis and Enterococcus faecalis). Results: Five new compounds derived from Carlina oxide were synthesized (IM8-IM12), and their structures were characterized by infrared (IR), 1H and 13C nuclear magnetic resonance (NMR). The new synthesized compounds were evaluated as mSpeB, DHFR from Enterococcus faecalis and DNA gyrase inhibitors by a docking analysis using MOE. These results show interesting ligand interactions with the three enzymes, and the best result was attributed to the complexes formed with IM9, which had the lowest score. Conclusion: In fact, these new compounds could lead to powerful approaches for the research and development of new antibiotics.

Published
2021

22. Dual‐State Emissive π‐Extended Salicylaldehyde Fluorophores: Synthesis, Photophysical Properties and First‐Principle Calculations

Author

Denis Frath, Timothée Stoerkler, Julien Massue, Denis Jacquemin, Gilles Ulrich, Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Frath, Denis

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Doping, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, Ring (chemistry), Photochemistry, 01 natural sciences, Fluorescence, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, Salicylaldehyde, Ab initio quantum chemistry methods, Intramolecular force, First principle, Moiety, Physical and Theoretical Chemistry
Abstract

International audience; The search for simple, low-cost, versatile, easily accessible, stimuli-responsive, highly emissive molecular fluorophores emitting both in solution and in the solid-state has prompted us to investigate the optical properties of a series of synthetically accessible salicyladehyde derivatives possessing a π-conjugated moiety at their 4-position. These dyes are mainly known as synthetic intermediates but can also display sizeable Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence owing to the presence of a 6-membered H-bonded ring in their structure. The photophysical properties of these compounds have been studied in solution (multiple solvents) and in the solid-state, as doped in PMMA films, leading to the observation of a pronounced fluorosolvatochromism. Modification of the spacer (ethynyl, vinyl or direct connection) involved the π-delocalization triggers major differences in terms of maximum emission wavelength and fluorescence quantum yields in the various media studied. All photophysical observations are rationalized by first-principle calculations.

Published
2021

23. Quinoline‐Based Silylium Ions: Synthesis, Structure and Lewis Acidity

Author

Frédéric Robert, Nivesh Kumar, Claire Laye, Yannick Landais, Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Silylation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Quinoline, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, chemistry.chemical_compound, Polymer chemistry, Lewis acids and bases, Physical and Theoretical Chemistry
Abstract

International audience; Heteroarylsilyl cations elaborated from a quinoline skeleton have been prepared from the corresponding silanes and their structures studied by 1 H, 29 Si, and 15 N NMR. DOSY experiments and DFT calculations were also carried out showing that the silyl cation center is stabilized intramolecularly by the quinoline nitrogen atom (N1), forming a highly strained and quasi planar 4-membered ring. Oxygenated and nitrogenated substituents at the C4 position on the quinoline ring were shown to reinforce the Si-N1 interaction through a p- conjugation. The Lewis acidity of this class of silylium was finally determined using Müller's nitrilium method.

Published
2021

24. Magnesium Complexes of Ladanein: A Beneficial Strategy for Stabilizing Polyphenolic Antivirals

Author

Mourad Elhabiri, Don Antoine Lanfranchi, Elisabeth Davioud-Charvet, Thomas Pietschmann, Xavier Martin-Benlloch, Sibylle Haid, TWINCORE, Zentrum für experimentelle und klinische Infektionsforschung GmbH,Feodor-Lynen Str. 7, 30625 Hannover, Germany., Laboratoire d'innovation moléculaire et applications (LIMA), 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), Centre for Experimental and Clinical Infection Research (TWINCORE), and Helmholtz Centre for Infection Research (HZI)-Medizinische Hochschule Hannover (MHH)

Subjects
Inorganic Chemistry, chemistry.chemical_classification, [SDV.SP.MED]Life Sciences [q-bio]/Pharmaceutical sciences/Medication, chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Magnesium, Polyphenol, Organic chemistry, chemistry.chemical_element, Flavones, ComputingMilieux_MISCELLANEOUS, 3. Good health
Abstract

Ladanein (noted FOMe) is a potent antiviral flavone that was shown to be active on a broad spectrum of enveloped viruses. This 5,6,7-trihydroxylated flavone has, however, pharmacokinetic properties and a half-life time that need to be improved for possible therapeutic applications. We herein took advantage of the complexation properties of ladanein (Fe(III)) to evaluate its ability to bind Mg(II) (biologically relevant and redox inert ion) precursors prepared beforehand from various carboxylic acids. The 5,6,7-trihydroxylated pattern of ladanein and the ligands borne by the Mg(II) atom of the precursors were found to be essential for firm Mg(II) binding. In particular, a ternary Mg(II) complex of ladanein and pidolate (noted FOMe.MgPid) was isolated and considered for its pharmacokinetic and virucidal (Hepatitis C Virus - HCV) properties. Mg(II) complexation significantly improved the physico-chemical (solubility) and the pharmacokinetic properties (clearance, plasmatic concentration) of the flavone FOMe, while not altering its anti-HCV capacity. Université de Strasbourg

Published
2021

25. Bolaamphiphile-based supramolecular gels with drugs eliciting membrane effects

Author

Denis Martinez, Antoine Loquet, Laurent Latxague, Ahmad Saad, Axelle Grélard, Birgit Habenstein, Philippe Barthélémy, Alexandra Gaubert, Estelle Morvan, Sébastien Benizri, James Tolchard, Acides Nucléiques : Régulations Naturelle et Artificielle (ARNA), Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut Européen de Chimie et Biologie (IECB), and Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Pyridones, [SDV]Life Sciences [q-bio], Membrane lipids, Supramolecular chemistry, Bolaamphiphile, macromolecular substances, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Biomaterials, Drug Delivery Systems, Colloid and Surface Chemistry, Furans, Lipid bilayer, ComputingMilieux_MISCELLANEOUS, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, technology, industry, and agriculture, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Membrane, Cancer cell apoptosis, Drug delivery, Self-healing hydrogels, Biophysics, lipids (amino acids, peptides, and proteins), 0210 nano-technology, Gels
Abstract

Supramolecular chemistry has garnered important interest in recent years toward improving therapeutic efficacy via drug delivery approaches. Although self-assemblies have been deeply investigated, the design of novel drugs leveraging supramolecular chemistry is less known. In this contribution, we show that a Low Molecular Weight Gel (LMWG) can elicit cancer cell apoptosis. This biological effect results from the unique supramolecular properties of a bolaamphiphile-based gelator, which allow for strong interaction with the lipid membrane. This novel supramolecular-drug paradigm opens up new possibilities for therapeutic applications targeting membrane lipids.

Published
2021

26. Multi‐Directional Mechanofluorochromism of Acetyl Pyrenes and Pyrenyl Ynones

Author

Laurent Michely, Arnaud Brosseau, Yuichi Hirai, Anna Makal, Davy-Louis Versace, Janusz Zakrzewski, Anna Wrona-Piotrowicz, Lucie Laize-Générat, Clémence Allain, Rémi Métivier, Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Department of Organic Chemistry [Łódź], Łódź University of Technology, Faculty of Chemistry [Warsaw], University of Warsaw (UW), Institut de Chimie et des Matériaux Paris-Est (ICMPE), and Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Trimethylsilyl, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Solid-state, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Fluorescence, Medicinal chemistry, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Bathochromic shift, Multi directional, Pyrene, Hypsochromic shift, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; A series of acetyl pyrenes and pyrenyl ynones with and without tert-butyl groups showed distinct mechanofluorochromism (MFC). Four pairs of polymorphic solids were found out of six compounds and interestingly, each of them showed hypsochromic, bathochromic or off-to-on MFC. The MFC properties were rationalized by categorizing the packing schemes into herringbone, sandwich, beta and gamma motifs depending on the relative contributions of C⋯C (or π-π) against C⋯H contacts. The bulky tertbutyl and trimethylsilyl groups served not only to reduce the number of aggregation patterns but also to prohibit the complete back reactions in solid state. Our results suggest that the simple pyrene derivatives may be promising candidates for a novel group of mechanically-sensitive materials.

Published
2021

27. Gold(I)-Catalyzed 7-exo-dig Cyclization: A Key Step to Access the Bicyclo[4.2.1]nonane Skeleton of Vibsatin A, a Neurotrophic Diterpenoid

Author

Marie-Isabelle Lannou, Janick Ardisson, Geoffroy Sorin, Luca Allievi, Rongyu Sun, Mohamed Selkti, Sabrina Dhambri, Cibles Thérapeutiques et conception de médicaments (CiTCoM - UMR 8038), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)

Subjects
Bicyclic molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Organic Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Silyl enol ether, 010402 general chemistry, 01 natural sciences, Biochemistry, Terpenoid, 0104 chemical sciences, Catalysis, Stereocenter, chemistry.chemical_compound, chemistry, Dig, Physical and Theoretical Chemistry, Nonane
Abstract

International audience; Vibsatin A is a new neurotrophic vibsane-type diterpenoid comprising a bridged bicyclo[4.2.1]nonane skeleton. Inspired by Sawamura’s works, we generated the bicyclic backbone through a Conia-ene-derived 7-exo-dig cyclization from an enantiomerically enriched TIPS-based silyl enol ether. The reaction, catalyzed by a sensitive gold(I) complex, was efficiently performed on a large scale by glovebox free techniques. Furthermore, the shape of this system was exploited for subsequent installation of all of the stereogenic centers.

Published
2021

28. Efficient Access to Arylated Aza‐ullazines by Regioselective Functionalization of their Pyridine Ring by H−Li Exchange and Electrophilic Substitution

Author

Philippe Pierrat, Pascal Boulet, Dhuaou Ibrahim, Philippe C. Gros, Laboratoire Lorrain de Chimie Moléculaire (L2CM), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Lorraine (UL), and Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Substitution (logic), Regioselectivity, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, 3. Good health, 0104 chemical sciences, Electrophilic substitution, chemistry.chemical_compound, Pyridine, Surface modification, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The regioselective functionalization of aza-ullazines has been successfully realized for the first time by either metalation using BuLi-containing aggregates (BuLi-LiDMAE) or electrophilic substitution. Mono and di-bromo-derivatives were obtained in good to excellent yields and further successfully converted into aryl and alkynyl azaullazine derivatives via Suzuki and Sonogashira cross-coupling reactions.

Published
2021

29. Phosphine‐Catalyzed Synthesis of Chiral N ‐Heterocycles through (Asymmetric) P(III)/P(V) Redox Cycling

Author

Charlotte Lorton, Nidal Saleh, Arnaud Voituriez, and Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Enantioselective synthesis, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Organocatalysis, Physical and Theoretical Chemistry, Redox cycling, Phosphine
Abstract

International audience; Phosphine-catalyzed tandem Michael addition/intramolecular Wittig reactions have been developed for the synthesis of chiral 2,5-dihydro-1H-pyrrole and tetrahydropyridine derivatives. These processes have been rendered catalytic in phosphine, thanks to the in situ reduction of phosphine oxide by phenylsilane. Furthermore, catalytic and asymmetric P(III)/P(V) processes were implemented using enantiopure chiral phosphines.

Published
2021

30. Quinolinonyl Non-Diketo Acid Derivatives as Inhibitors of HIV-1 Ribonuclease H and Polymerase Functions of Reverse Transcriptase

Author

Nicole Grandi, Enzo Tramontano, Francesca Esposito, Davide Ialongo, Alessandro De Leo, Giorgio Amendola, Daniela De Vita, Antonella Messore, Valentina Noemi Madia, Marie-Line Andreola, Ettore Novellino, Mathieu Métifiot, Sandro Cosconati, Roberta Costi, Angela Corona, Roberto Di Santo, Valeria Tudino, Francesco Saccoliti, Luigi Scipione, Microbiologie Fondamentale et Pathogénicité [Bordeaux] (MFP), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Messore, A., Corona, A., Madia, V. N., Saccoliti, F., Tudino, V., De Leo, A., Ialongo, D., Scipione, L., De Vita, D., Amendola, G., Novellino, E., Cosconati, S., Metifiot, M., Andreola, M. -L., Esposito, F., Grandi, N., Tramontano, E., Costi, R., and Di Santo, R.

Subjects
Quinolone, Anti-HIV Agents, Microbial Sensitivity Tests, Quinolones, HeLa Cell, Virus Replication, 01 natural sciences, Article, 03 medical and health sciences, Drug Discovery, Humans, Ribonuclease H, Human Immunodeficiency Viru, Magnesium, AIDS, HIV, rNase H inhibitors, Quinolinonyl non-diketo acid derivatives, RNase H, ComputingMilieux_MISCELLANEOUS, Polymerase, 030304 developmental biology, chemistry.chemical_classification, 0303 health sciences, biology, Microbial Sensitivity Test, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Anti-HIV Agent, Reverse transcriptase, Reverse Transcriptase Inhibitor, 3. Good health, 0104 chemical sciences, Amino acid, Integrase, Molecular Docking Simulation, 010404 medicinal & biomolecular chemistry, Ribonuclease H, Human Immunodeficiency Virus, Enzyme, Biochemistry, Viral replication, Docking (molecular), Mutation, [SDV.MP.VIR]Life Sciences [q-bio]/Microbiology and Parasitology/Virology, HIV-1, Mutagenesis, Site-Directed, biology.protein, Reverse Transcriptase Inhibitors, Molecular Medicine, Human, HeLa Cells, Protein Binding
Abstract

Novel anti-HIV agents are still needed to overcome resistance issues, in particular inhibitors acting against novel viral targets. The ribonuclease H (RNase H) function of the reverse transcriptase (RT) represents a validated and promising target, and no inhibitor has reached the clinical pipeline yet. Here, we present rationally designed non-diketo acid selective RNase H inhibitors (RHIs) based on the quinolinone scaffold starting from former dual integrase (IN)/RNase H quinolinonyl diketo acids. Several derivatives were synthesized and tested against RNase H and viral replication and found active at micromolar concentrations. Docking studies within the RNase H catalytic site, coupled with site-directed mutagenesis, and Mg2+ titration experiments demonstrated that our compounds coordinate the Mg2+ cofactor and interact with amino acids of the RNase H domain that are highly conserved among naïve and treatment-experienced patients. In general, the new inhibitors influenced also the polymerase activity of RT but were selective against RNase H vs the IN enzyme.

Published
2021

31. Modulation of Cellular Fate of Vinyl Triarylamines through Structural Fine Tuning: To Stay or Not To Stay in the Mitochondria?

Author

Marie-Paule Teulade-Fichou, Delphine Naud-Martin, Rahima Chennoufi, Sounderya Nagarajan, Eric Deprez, Aude Sourdon, Florence Mahuteau-Betzer, Florent Poyer, Laura Fourmois, Chimie et modélisation pour la biologie du cancer (CMBC), Institut Curie [Paris]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de biologie et pharmacologie appliquée (LBPA), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), and Mahuteau-Betzer, Florence

Subjects
Mitochondrial DNA, Chemical biology, Context (language use), Mitochondrion, 01 natural sciences, Biochemistry, 03 medical and health sciences, chemistry.chemical_compound, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Inner mitochondrial membrane, Molecular Biology, 030304 developmental biology, 0303 health sciences, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Depolarization, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Mitochondria, 0104 chemical sciences, Nuclear DNA, Biophysics, Molecular Medicine, DNA
Abstract

International audience; Mitochondria is involved in many cellular pathways and dysfunctional mitochondria are linked to various diseases. Hence efforts have been driven to design mitochondria-targeted fluorophores for monitoring the mitochondria status. However, the factors that govern the mitochondria-targeted potential of dyes are not well-understood. In this context, we synthesized analogues of the TP-2Bzim probe belonging to the vinyltriphenylamine (TPA) class and already described for its capacity to bind nuclear DNA in fixed cells and mitochondria in live cells. These analogues (TP-1Bzim, TP n-2Bzim, TP 1+-2Bzim, TN-2Bzim) differ by the cationic charge, the number of vinylbenzimidazolium branches and the nature of the triaryl core. Using microscopy, we demonstrated that the cationic derivatives accumulate in mitochondria but do not reach mtDNA. Under depolarisation of the mitochondrial membrane, TP-2Bzim and TP 1+-2Bzim translocate to the nucleus in direct correlation with their strong DNA affinity. This reversible phenomenon emphasizes that these probes can be used to monitor ΔΨm variations.

Published
2021

32. Gold(I)-catalyzed divergent and diastereoselective synthesis of azepines by ammoniumation/ring-expansion reactions

Author

Patrick Pale, Romain Pertschi, Aurélien Blanc, Jean-Marc Weibel, Nicolas Kern, Solène Miaskiewicz, Institut de Chimie de Strasbourg, and Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Ammoniumation, Bicyclic molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Azetidine, Gold(I), Azepines, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Cyclobutane, chemistry.chemical_compound, Nucleophile, Azetidines, General Earth and Planetary Sciences, Azepine, Pharmacophore, Ring Expansion, General Environmental Science
Abstract

Summary Gold(I) catalysts enable the chemoselective addition of tailor-made N-sulfonylated azetidine derivatives onto alkynes, affording bicyclic vinyl-ammonium gold intermediates. Intramolecularly intercepted by an adequately positioned nucleophilic carbonate or ester function, these ammoniums efficiently lead to ring-expanded azepine products, which are important pharmacophore fragments. Depending on the substitution pattern of the starting material, divergent deauration pathways occur, stereoselectively producing monomeric or original dimeric nitrogenated seven-membered rings in good to excellent yields, such as cis-tetrahydroazepin-4,5-diol carbonate, (E)-alkylidene tetrahydroazepin-4-yl ester, and cis-bis(azepinyl)cyclobutane derivatives. One of the synthetic methods was extended to the formation of dihydrobenzazepines of high pharmaceutical value. A mechanistic study including kinetics and labeling experiments allowed us to fully understand the origin of the high chemo- and diastereoselectivity of these rearrangements. Overall, this work demonstrates the underlying synthetic potential of the ammoniumation catalyzed by gold for the future development of reaction cascades and preparation of bioactive compounds.

Published
2021

33. Dual Electroactivity in a Covalent Organic Network with Mechanically Interlocked Pillar[5]arenes

Author

Thomas Devic, Charlotte Martineau-Corcos, Joël Gaubicher, Philippe Poizot, Vincent Sarou-Kanian, Benoit Colasson, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)

Subjects
Rotaxane, viologen, Mechanical bond, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Pillar, Viologen, General Chemistry, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, Covalent bond, Polymer chemistry, medicine, covalent-organic network, rotaxane, Structure based, electroactive solid, pillar[5]arene, medicine.drug
Abstract

International audience; The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material.

Published
2021

34. Thiazolo[5,4‐ f ]quinoxalines, Oxazolo[5,4‐ f ]quinoxalines and Pyrazino[ b,e ]isatins: Synthesis from 6‐Aminoquinoxalines and Properties

Author

Laurent Picot, Joshua M. Sims, Valérie Thiéry, William Erb, Vincent Dorcet, Florence Mongin, Olivier Mongin, Thierry Roisnel, Nour El Osmani, Frédéric Lassagne, Thomas Robert, Ziad Fajloun, Stéphane Bach, Nicolas Richy, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Libanaise, LIttoral ENvironnement et Sociétés (LIENSs), La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS), Assistance Publique - Hôpitaux de Marseille (APHM), Fédération de recherche de Roscoff (FR2424), Station biologique de Roscoff (SBR), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Biologie Intégrative des Modèles Marins (LBI2M), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Station biologique de Roscoff (SBR), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 'Comité d'Ille et Vilaine 35' de la Ligue Nationale Contre le Cancer, Université de Rennes 1, Centre National de la Recherche Scientifique, Fonds Européen de Développement Régional (FEDER, D8 VENTURE Bruker AXS diffractometer), IBiSA (French Infrastructures en Sciences du Vivant: Biologie, Santé et Agronomie), Cancéropôle Grand Ouest ('Marines molecules, metabolism and cancer' network), Biogenouest (Western France Life Science and Environment Core Facility Network), FR2424, CNRS, Sorbonne UniversitéRoscoff, France, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Ecole Doctorale des Sciences et de la Technologie (EDST), Lebanese University [Beirut] (LU), LIttoral ENvironnement et Sociétés - UMR 7266 (LIENSs), Institut national des sciences de l'Univers (INSU - CNRS)-La Rochelle Université (ULR)-Centre National de la Recherche Scientifique (CNRS), Institut Polytechnique de Paris (IP Paris), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), LIttoral ENvironnement et Sociétés - UMRi 7266 (LIENSs), and Université de La Rochelle (ULR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Quinoxaline, Alkyne, Sonogashira coupling, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, Oxazole, chemistry.chemical_compound, Regioselectivity, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, chemistry.chemical_classification, Kinase inhibitor, Iodination, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Halogenation, 3. Good health, 0104 chemical sciences, chemistry, Azole
Abstract

International audience; The regioselective iodination of different 2-mono-, 3-mono- and 2,3-disubstituted 6-aminoquinoxalines, which takes place at their 5-position, was rationalized on the basis of Hückel theory calculations. Oxazolo- and thiazolo[5,4-f]quinoxaline analogues of reported disease-related protein kinases inhibitors were synthesized from the obtained 6-amino-5-iodoquinoxalines by using as key step copper-catalyzed azole ring formation. Pyrazino[b,e]isatins were obtained, for the first time, from the same substrates by recourse to Sonogashira coupling, alkyne hydration, and oxidative cyclization. The absorption and emission properties of the most promising compounds were recorded. In addition, most of the synthesized polycycles were evaluated as protein kinase inhibitors and for their antiproliferative activity towards cancer cells.

Published
2021

35. Heterohelicenes through 1,3-Dipolar Cycloaddition of Sydnones with Arynes: Synthesis, Origins of Selectivity, and Application to pH-Triggered Chiroptical Switch with CPL Sign Reversal

Author

Davide Audisio, Expédite Yen-Pon, Floris Buttard, Pierre Thuéry, Lucas Frédéric, Pier Alexandre Champagne, Grégory Pieters, Frédéric Taran, Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Department of Chemistry and Environmental Science, New Jersey Institute of Technology, University Heights-New Jersey Institute of Technology [Newark] (NJIT), Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ANR-17-CE07-0035,Mesacco,Accès à des structures p-conjugués complexes par la chimie des composés mésoioniques(2017), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Protonation, 010402 general chemistry, 1-3-dipolar cycloadditions, DFT, 01 natural sciences, Aryne, Article, chemistry.chemical_compound, [CHIM.CRIS]Chemical Sciences/Cristallography, Reactivity (chemistry), 1,3-dipolar cycloadditions, QD1-999, arynes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Regioselectivity, circularly polarized luminescence, Cycloaddition, 0104 chemical sciences, Chemistry, Crystallography, Helicene, chemistry, 1,3-Dipolar cycloaddition, mesoionics, Density functional theory
Abstract

International audience; Regioselective access to heterohelicenes through the 1,3-dipolar cycloaddition of sydnones with arynes is described. Novel access to sydnones and poly(hetero)aromatic aryne precursors allowed the introduction of chemical diversity over multiple positions of the helical scaffolds. The origins of the unconventional regioselectivity during the cycloaddition steps was systematically investigated using density functional theory (DFT) calculations, unveiling the key features that control this reactivity, namely, face-to-face ($\pi \cdot \cdot \cdot \pi$) or edge-to-face (C−H$\cdot \cdot \cdot \pi$) interactions, primary orbital interactions and distortion from coplanarity in the transition structures (TSs) of the transformation. From the library of 24 derivatives synthesized, a pyridyl containing derivative displayed reversible, red-shifted, pH-triggered chiroptical switching properties, with CPL-sign reversal. It is found that protonation of the helicene causes a change of the angle between the electric and magnetic dipole moments related to the S$_1$ → S$_0$ transition, resulting in this rare case of reversible CPL sign inversion upon application of an external stimulus.

Published
2021

36. Designing Active Sites for Structure-Sensitive Reactions via the Generalized Coordination Number: Application to Alcohol Dehydrogenation

Author

Kamila Kaźmierczak, Ruben Staub, Carine Michel, Noémie Perret, Paul Clabaut, Stephan N. Steinmann, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), IRCELYON-C'Durable (CDURABLE), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Materials science, biology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Coordination number, Structure (category theory), Active site, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, General Energy, chemistry, Computational chemistry, biology.protein, Dehydrogenation, Metal catalyst, Physical and Theoretical Chemistry, Scaling
Abstract

fff; International audience; Identifying the structure of the most active site is essential to improve the performance of supported metal catalysts. For structure-sensitive reactions, in silico design cannot be easily achieved combining the scaling relations and Brønsted–Evans–Polanyi relations, which are only built on energy-based descriptors. We used here the generalized coordination number as a structural descriptor and established that low-coordinated sites are desirable when using Co and Cu to perform the acceptor-less alcohol dehydrogenation reaction.

Published
2021

37. Flavin‐Helicene Amphiphilic Hybrids: Synthesis, Characterization, and Preparation of Surface‐Supported Films

Author

Adrianna Cytryniak, Renata Bilewicz, Jan Storch, Jeanne Crassous, Radek Cibulka, Ivana Císařová, Martin Jakubec, Jan Vacek, Jan Hrbac, David Novak, Ludovic Favereau, Martina Zatloukalová, Jaroslav Žádný, Institute of Chemical Process Fundamentals (ICPF), Czech Academy of Sciences [Prague] (CAS), Palacky University Olomouc, Charles University [Prague] (CU), University of Chemistry and Technology Prague (UCT Prague), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Warsaw (UW), Masaryk University [Brno] (MUNI), Palacky University [RVO 61989592], Ministry of Education, Youth and Sports (MEYS, Czech Republic) [IGA_LF_2020_022], Czech Science Foundation Grant Agency of the Czech Republic [20-19353S], MEYS [CZ.02.2.69/0.0/0.0/16_027/0008482], project \'e-Infrastruktura CZ\' within the program \'Projects of Large Research, Development and Innovations Infrastructures\' within the program \'Projects of Large Research, Development and Innovations Infrastructures\' [eINFRA LM2018140], Institute of Chemical Process Fundamentals of the ASCR, Czech Republic, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Circular dichroism, thin layers, lipidic cubic phases, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Supramolecular chemistry, Mesophase, General Chemistry, Flavin group, 010402 general chemistry, flavins, 01 natural sciences, 0104 chemical sciences, helicenes, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry.chemical_compound, Helicene, Amphiphile, [CHIM]Chemical Sciences, Molecule, Cyclic voltammetry, redox behavior
Abstract

International audience; This work reports on the preparation and structural characterization of flavo[7]helicene 1 (flavin-[7]helicene conjugate), which was subsequently characterized at the molecular level in either an aqueous environment or an organic phase, at the supramolecular level in the form of polymeric layers, and also embedded in a lipidic mesophase environment to study the resulting properties of such a hybrid relative to its parent molecules. The flavin benzo[g]pteridin-2,4-dione (isoalloxazine) was selected for conjugation because of its photoactivity and reversible redox behavior. Compound 1 was prepared from 2-nitroso[6]helicene and 6-methylamino-3-methyluracil, and characterized using common structural and spectroscopic tools: circular dichroism (CD), circularly polarized luminescence (CPL) spectroscopy, cyclic voltammetry (CV), and DFT quantum calculations. In addition, a methodology that allows the loading of 1 enantiomers into an internally nanostructured lipid (1-monoolein) matrix was developed.

Published
2021

38. Dissection of the anti-Candida albicans mannan immune response using synthetic oligomannosides reveals unique properties of β-1,2 mannotriose protective epitopes

Author

Sébastien Damiens, Faustine Dubar, Samir Jawhara, Boualem Sendid, Mayeul Collot, Karine Lecointe, Jean-Maurice Mallet, Anne-Sophie Drucbert, Daniel Poulain, Chantal Fradin, Pierre-Marie Danzé, Jean-Pierre Vilcot, Jérôme de Ruyck, Frédéric Grenouillet, Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Facteurs de Risque et Déterminants Moléculaires des Maladies liées au Vieillissement - U 1167 (RID-AGE), Institut Pasteur de Lille, Réseau International des Instituts Pasteur (RIIP)-Réseau International des Instituts Pasteur (RIIP)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Optoélectronique - IEMN (OPTO - IEMN), INSA Institut National des Sciences Appliquées Hauts-de-France (INSA Hauts-De-France), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Centre Hospitalier Régional Universitaire de Besançon (CHRU Besançon), We thank the European Union for funding through the INTERREG V France—Wallonie—Vlaanderen program—SmartBioControl-BIOSENS project and the Programme Hospitalier de Recherche Clinique, CandiGene, 2011–1918., Unité de Glycobiologie Structurale et Fonctionnelle (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire des biomolécules [LBM UMR 7203], Institut de Pathologie [CHU Lille], Laboratoire de Bioimagerie et Pathologies [LBP], Médicaments et biomatériaux à libération contrôlée: mécanismes et optimisation - Advanced Drug Delivery Systems - U 1008 [MBLC - ADDS], Lille Inflammation Research International Center - U 995 [LIRIC], Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN], Laboratoire Chrono-environnement (UMR 6249) [LCE], Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 [UGSF], and Collot, Mayeul

Subjects
Antigens, Fungal, medicine.drug_class, [SDV]Life Sciences [q-bio], Science, Immunology, Oligosaccharides, Monoclonal antibody, Biochemistry, Microbiology, Article, Epitope, Mannans, 03 medical and health sciences, Antigen, Antibody Specificity, Candida albicans, medicine, 030304 developmental biology, Mannan, 0303 health sciences, Multidisciplinary, biology, 030306 microbiology, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Candidiasis, Antibodies, Monoclonal, Surface Plasmon Resonance, [CHIM.ORGA] Chemical Sciences/Organic chemistry, biology.organism_classification, Chemical biology, Corpus albicans, 3. Good health, [SDV] Life Sciences [q-bio], Polyclonal antibodies, biology.protein, Medicine, Antibody, Trisaccharides, Epitope Mapping
Abstract

Candida albicans mannan consists of a large repertoire of oligomannosides with different types of mannose linkages and chain lengths, which act as individual epitopes with more or less overlapping antibody specificities. Although anti-C. albicans mannan antibody levels are monitored for diagnostic purposes nothing is known about the qualitative distribution of these antibodies in terms of epitope specificity. We addressed this question using a bank of previously synthesized biotin sulfone tagged oligomannosides (BSTOs) of α and β anomery complemented with a synthetic β-mannotriose described as a protective epitope. The reactivity of these BSTOs was analyzed with IgM isotype monoclonal antibodies (MAbs) of known specificity, polyclonal sera from patients colonized or infected with C. albicans, and mannose binding lectin (MBL). Surface plasmon resonance (SPR) and multiple analyte profiling (MAP) were used. Both methods confirmed the usual reactivity of MAbs against either α or β linkages, excepted for MAb B6.1 (protective epitope) reacting with β-Man whereas the corresponding BSTO reacted with anti-α-Man. These results were confirmed in western blots with native C. albicans antigens. Using patients’ sera in MAP, a significant correlation was observed between the detection of anti-mannan antibodies recognizing β- and α-Man epitopes and detection of antibodies against β-linked mannotriose suggesting that this epitope also reacts with human polyclonal antibodies of both specificities. By contrast, the reactivity of human sera with other α- and β-linked BSTOs clearly differed according to their colonized or infected status. In these cases, the establishment of an α/β ratio was extremely discriminant. Finally SPR with MBL, an important lectin of innate immunity to C. albicans, classically known to interact with α-mannose, also interacted in an unexpected way with the protective epitope. These cumulative data suggest that structure/activity investigations of the finely tuned C. albicans anti-mannose immune response are worthwhile to increase our basic knowledge and for translation in medicine.

Published
2021

39. Platform molecule from sustainable raw materials; case study succinic acid

Author

Rawa Abdallah, Hayet Djelal, Abdeltif Amrane, Florence Fourcade, Alaa Salma, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), UniLaSalle Rennes - Ecole des Métiers de l'Environnement, UniLaSalle, Université Libanaise, Municipality of Bebnine, North-Lebanon through the Education Program of Lebanese students, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Succinic acid production, Downstream separation methods, Computer science, 020209 energy, General Chemical Engineering, Platform molecules, Biomass, 02 engineering and technology, Raw material, 7. Clean energy, chemistry.chemical_compound, 020401 chemical engineering, Processing technology, 0202 electrical engineering, electronic engineering, information engineering, Production (economics), 0204 chemical engineering, [CHIM.ORGA]Chemical Sciences/Organic chemistry, business.industry, Fossil fuel, Renewable energy, chemistry, 13. Climate action, Succinic acid, Fermentation, Biochemical engineering, Redox potential, business
Abstract

International audience; Platform molecules were defined by the US Department of Energy, as bio-based or bio-derived chemicals whose constituting elements totally originated from biomass and could be used as building blocks for the production of commodity and refined chemicals. These chemicals can subsequently be converted into a number of high-value bio-based chemicals or materials. Today, there is a growing urge for the discovering of a cheaper and cleaner way for the environment to produce platform molecules from renewable substrate such as carbon. Succinic acid (SA) is considered as a key platform chemical since it is used as a precursor for other valuable chemicals and has aroused interest worldwide with its wide applications. This review aims at highlighting the currently available information about the mechanisms involved in the production of platform molecules, especially the SA production. In this review, the processing technologies used in the production of platform molecules are described, in addition to the information regarding the optimization of key parameters, the mechanisms of genetic engineering and finally the redox potential and purification processes which are known as alternative cost-competitive providers of fossil fuels.

Published
2021

40. Electrochemical TEMPO-Catalyzed Oxidative Ugi-Type Reaction

Author

Na Pan, Maegan Xinen Lee, Maxime R. Vitale, Laurence Grimaud, Louis Bunel, Laboratoire des biomolécules (LBM UMR 7203), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), East China Normal University [Shangaï] (ECNU), and VITALE, Maxime R.

Subjects
Cultural Studies, History, Literature and Literary Theory, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Isocyanide, Organic chemistry, Oxidative phosphorylation, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Electrosynthesis, Electrochemistry, Combinatorial chemistry, Indirect anodic oxidation, Catalysis, chemistry.chemical_compound, QD241-441, Oxidative Ugi reaction, TEMPO, human activities, Inorganic chemistry, Muticomponent reaction, QD146-197
Abstract

International audience; Oxidative isocyanide-based multicomponent reactions (oxidative IMCRs) are very useful tools for the rapid construction of molecular diversity starting from readily available and stable substrates. Despite all their benefits, such multicomponent reactions are underdeveloped and strictly limited to 3component processes. Indeed, in the presence of several reaction partners, the oxidation event needs to be rigorously chemoselective, which becomes incredibly more intricate as the number of reactive components increases. Nonetheless, we could overcome this significant pitfall and reach the first oxidative Ugi-type 4-IMCR by capitalizing on a very mild and green TEMPO-catalyzed electro-oxidation process. Employing alcohols as aldehyde surrogates and in the notable absence of any supporting electrolyte, this transformation proved to be extremely chemoselective in the presence of an amine and was compatible with a wide range of alcohols, amines, isocyanides, and carboxylic acids.

Published
2021

41. Catalytic Intermolecular C(sp3)–H Amination: Selective Functionalization of Tertiary C–H Bonds vs Activated Benzylic C–H Bonds

Author

Philippe Dauban, Erwan Brunard, Elsa Van Elslande, Tanguy Saget, Vincent Boquet, Institut de Chimie des Substances Naturelles (ICSN), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, digestive, oral, and skin physiology, Intermolecular force, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Surface modification, Amination
Abstract

International audience; A catalytic intermolecular amination of non-activated tertiary C(sp 3)−H bonds (BDE of 96 kcal.mol-1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal.mol-1). The tertiary C(sp 3)−H bond is selectively functionalized to afford a,a,a-trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(Stfpttl)4, a rhodium(II) complex with a well-defined catalytic pocket, with tert-butylphenol sulfamate (TBPhsNH2), which leads to a discriminating rhodium-bound nitrene species under mild oxidative conditions. This catalytic system is very robust and the reaction was performed on a 50 mmoles-scale with only 0.01 mol% of catalyst. The TBPhs group can be removed under mild conditions to afford the corresponding NH-free amines.

Published
2021

42. Para‐Functionalization of N‐Substituted 4‐amino[2.2]paracyclophanes by Regioselective Formylation

Author

Laurent Micouin, Simon Felder, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), and Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Regioselectivity, Planar chirality, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Formylation, Surface modification, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

43. Industrial Ramie Growing on Reclaimed Ion-Adsorption Rare Earth Elements Mine Tailings in Southern China: Defibration and Fibers Quality

Author

Rongliang Qiu, Hermine Huot, Isabelle Zigler-Devin, Chang Liu, Jean-Louis Morel, Ye-Tao Tang, Mahdi Hedri, Nicolas Brosse, César Segovia, Laboratoire d'Etude et de Recherche sur le Matériau Bois (LERMAB), Université de Lorraine (UL), Laboratoire Sols et Environnement (LSE), Université de Lorraine (UL)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Sun Yat-Sen University [Guangzhou] (SYSU), Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, and ANR-11-LABX-0002,ARBRE,Recherches Avancées sur l'Arbre et les Ecosytèmes Forestiers(2011)

Subjects
0106 biological sciences, Environmental Engineering, 020209 energy, rare earth elements, phytoremediation, 02 engineering and technology, degumming, 01 natural sciences, [SPI.MAT]Engineering Sciences [physics]/Materials, Ramie, 010608 biotechnology, Ultimate tensile strength, 0202 electrical engineering, electronic engineering, information engineering, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Fiber, Waste Management and Disposal, Natural fiber, Steam explosion, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, Alkali metal, Tailings, steam explosion, Phytoremediation, [CHIM.POLY]Chemical Sciences/Polymers, ramie, Nuclear chemistry
Abstract

International audience; Ramie plants (Boehmeria nivea) have been cultivated on ion-adsorption rare earth elements (REEs) mine tailings and showed a low ability to accumulate REEs, especially in the stems (REE= 24±17 mg kg-1) with higher concentration in leaves and roots (REE= 57 to 66 mg kg-1). Ramie individual fibers were isolated using three degumming processes: a traditional alkali treatment (AT), a steam explosion (SE) treatment after a neutral (SEN) or after a basic (SEB) impregnation. Cellulose-rich (> 80%) fine fibers with very low amounts of non-cellulosic sugars (

Published
2021

44. Oxidative additions of alkynyl/vinyl iodides to gold and gold-catalyzed vinylation reactions triggered by the MeDalphos ligand†

Author

Jéssica Rodríguez, Alexis Tabey, Sonia Mallet-Ladeira, Didier Bourissou, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Plateforme de l'Institut de chimie de Toulouse, Université de Toulouse (UT), ANR-19-CE07-0037,Gold-III,Chimie de l'or(III)(2019), 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 Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Chimie de Toulouse (ICT-FR 2599), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)

Subjects
Steric effects, 010405 organic chemistry, Ligand, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, organic chemicals, technology, industry, and agriculture, Substrate (chemistry), General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, macromolecular substances, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Oxidative addition, 0104 chemical sciences, 3. Good health, Catalysis, chemistry.chemical_compound, Chemistry, chemistry, Yield (chemistry), Chemoselectivity
Abstract

The hemilabile Ad2P(o-C6H4)NMe2 ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold. The reaction is general. It works with a broad range of substrates of various electronic bias and steric demand, and proceeds with complete retention of stereochemistry from Z and E vinyl iodides. Both alkynyl and vinyl iodides react faster than aryl iodides. The elementary step is amenable to catalysis. Oxidative addition of vinyl iodides to gold and π-activation of alkenols (and N-alkenyl amines) at gold have been combined to achieve hetero-vinylation reactions. A number of functionalized heterocycles, i.e. tetrahydrofuranes, tetrahydropyranes, oxepanes and pyrrolidines were obtained thereby (24 examples, 87% average yield). Taking advantage of the chemoselectivity for vinyl iodides over aryl iodides, sequential transformations involving first a hetero-vinylation step and then a C–N coupling, a C–C coupling or an heteroarylation were achieved from a vinyl/aryl bis-iodide substrate., The hemilabile Ad2P(o-C6H4)NMe2 ligand promotes fast, quantitative and irreversible oxidative addition of alkynyl and vinyl iodides to gold.

Published
2021

45. Coupling Electrocatalytic CO 2 Reduction with Thermocatalysis Enables the Formation of a Lactone Monomer

Author

Sarah Lamaison, David W. Wakerley, Thibault Cantat, Emmanuel Nicolas, Ngoc Huan Tran, Louise Ponsard, Marc Fontecave, Chaire Chimie des processus biologiques, Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), doctoral fellowship from Le Corps des Ponts, des Eaux et des Forêts, Foundation of the Collège de France, Marie Curie Prestige Fellowship, European Project: 768919,CARBON4PUR, European Project: ERC CoG n°818260 ,ReNewHydrides, Collège de France - Chaire Chimie des processus biologiques, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Electrolytic cell, General Chemical Engineering, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Polyester, chemistry.chemical_compound, General Energy, Monomer, chemistry, Environmental Chemistry, General Materials Science, Propylene oxide, 0210 nano-technology, Bimetallic strip, Carbonylation, Faraday efficiency
Abstract

International audience; Carbonylation reactions that generate high-value chemical feedstocks are integral to the formation of many industrially significant compounds. However, these processes require the use of CO, which is invariably derived from fossil-fuelreforming reactions. CO may also be generated through the electroreduction of CO2, but the coupling of these two processes is yet to be considered. Merging electrocatalytic reduction of CO2 to CO with thermocatalytic use of CO would expand the range of the chemicals produced from CO2. This work describes for the first time the development of a system coupling a high-pressure CO2 electrolytic cell containing a bimetallic ZnAg catalyst at the cathode for production of CO with a reactor with a faradaic efficiency of >90 % where high pressure CO is used for carbonylating propylene oxide into β-butyrolactone by thermal catalysis, the latter step having a reaction yield above 80%. While the production of monomers and polymers from CO2 is currently limited to organic carbonates, this strategy opens up the access to lactones from CO2, for the formation of polyesters.

Published
2021

46. Butterfly‐like Shape Liquid Crystals Based Fused‐Thiophene as Unidimensional Ambipolar Organic Semiconductors with High Mobility

Author

Bi-Qin Wang, Hirosato Monobe, Tao Ma, Yu-Jie Zhong, Bertrand Donnio, Ke-Qing Zhao, Ping Hu, Hai-Feng Wang, Sichuan Normal University (SNU), National Institute of Advanced Industrial Science and Technology [Tokyo] (AIST), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), National Institute of Advanced Industrial Science and Technology (AIST), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Donnio, Bertrand

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, business.industry, Ambipolar diffusion, Chemistry, Mesogen, Organic Chemistry, Mesophase, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Organic semiconductor, Crystallography, Semiconductor, Liquid crystal, Charge carrier, business, Luminescence
Abstract

Mesomorphous butterfly-like shape molecules based on benzodithiophene, benzodithiophene-4,8-dione and cyclopentadithiophen-4-one core moieties were efficiently synthesized by the Suzuki-Miyaura coupling and Scholl oxidative cyclo-dehydrogenation reactions' tandem. Most of the butterfly molecules spontaneously self-organize into columnar hexagonal mesophase. The electron-deficient systems possess strong solvent-gelling ability but are not luminescent, whereas the electron-rich terms do not form gels but strongly emit light between 400 and 600 nm. The charge carrier mobility was also measured by time-of-flight transient photocurrent technique in the mesophases for some of the compounds. They display hole-transport performances with positive charge mobility in the 10 -3 cm -2 V -1 s -1 range, consistent with the high degree of ordering and stability of the columnar superstructures. One mesogen in particular with benzodithiophen-4,8-dione core shows outstanding ambipolar charge carrier transport with both high electron (μe = 6.6×10 -3 cm -2 V -1 s -1 ) and hole (μh = 4.5×10 -3 cm -2 V -1 s -1 ) mobility values.

Published
2021

47. Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Author

Christiane André-Barrès, Michel Baron, Alain Chamayou, Lori Gonnet, Michel Baltas, Brigitte Guidetti, Tohru Sato, Rachel Calvet, Jean-Claude Micheau, Centre de recherche d'Albi en génie des procédés des solides divisés, de l'énergie et de l'environnement (RAPSODEE), IMT École nationale supérieure des Mines d'Albi-Carmaux (IMT Mines Albi), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Centre National de la Recherche Scientifique (CNRS), Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interactions moléculaires et réactivité chimique et photochimique (IMRCP), 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 Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Kyoto University [Kyoto], Centre National de la Recherche Scientifique (CNRS)-IMT École nationale supérieure des Mines d'Albi-Carmaux (IMT Mines Albi), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), IDeAS - Interfaces Dynamiques et Assemblages Stimulables (IDeAS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Kyoto University, CNRS, University Paul Sabatier, IMT Mines Albi, and JSPS

Subjects
General Chemical Engineering, Kinetics, 02 engineering and technology, Activation energy, 010402 general chemistry, 01 natural sciences, Chemical kinetics, Diels−Alder, chemistry.chemical_compound, Computational chemistry, Mechanochemistry, Mechanisms, Environmental Chemistry, Maleimide, Diels–Alder reaction, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Ball-milling, 0104 chemical sciences, Solvent, Reagent, 0210 nano-technology
Abstract

International audience; The Diels–Alder reaction kinetics between diphenylfulvene and maleimide using mechanochemistry and in liquid state is described. This reaction was carried out in solid state using a modified vibratory ball-mill with temperature control and in solution with toluene as solvent. The effect of temperature, ball mass, material, additives, and aging reaction were studied. We reported for the first time the kinetics of a mechanochemical reaction depending on the ratio ball mass/mass of the reagent. A new kinetic model has been established that corresponds well to our experimental data and allows an estimation of the global activation energy. In solution, the retro Diels–Alder reaction was observed. The reaction was second order for the formation of endo and exo and first order for the retro Diels–Alder reaction. The grinding method shows many advantages compared to solution: shorter reaction time, total reaction, and better selectivity.

Published
2021

48. Butterfly Mesogens Based on Carbazole, Fluorene or Fluorenone: Mesomorphous, Gelling, Photophysical, and Photoconductive Properties

Author

Hirosato Monobe, Ke-Qing Zhao, Bertrand Donnio, Hang Junfang, Bi-Qin Wang, Chenhui Zhu, Lin Hang, Ping Hu, Sichuan Normal University (SNU), National Institute of Advanced Industrial Science and Technology [Tokyo] (AIST), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Photocurrent, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Carbazole, Photoconductivity, Organic Chemistry, 02 engineering and technology, Fluorene, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Fluorescence, 0104 chemical sciences, Organic semiconductor, chemistry.chemical_compound, Fluorenone, chemistry, Yield (chemistry), Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; A generic synthetic method based on the Suzuki-Scholl reactions was successfully exploited to yield new poly(hetero)aromatic hydrocarbons containing carbazole, fluorene or fluorenone moieties. These butterfly-like mesogens exhibit columnar mesophases, form fibrous gels in various solvents, emit blue to orange light in films and solutions and show outstanding photocurrent behavior with charge carrier mobility in the ∼0.03 cm 2 V −1 s −1 range.

Published
2021

49. Interplay between a Foldamer Helix and a Macrocycle in a Foldarotaxane Architecture

Author

Ivan Huc, Yann Ferrand, Maxime Gauthier, Frédéric Coutrot, Caroline Clavel, Brice Kauffmann, Victor Koehler, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut Européen de Chimie et Biologie (IECB), and Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
Steric effects, Rotaxane, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Supramolecular chemistry, Foldamer, General Chemistry, Nuclear magnetic resonance spectroscopy, General Medicine, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Axle, Crystallography, Helix, Molecular motion, ComputingMilieux_MISCELLANEOUS
Abstract

The design and synthesis of a novel rotaxane/foldaxane hybrid architecture is reported. The winding of an aromatic oligoamide helix host around a dumbbell-shaped thread-like guest, or axle, already surrounded by a macrocycle was evidenced by NMR spectroscopy and X-ray crystallography. The process proved to depend on the position of the macrocycle along the axle and the associated steric hindrance. The macrocycle thus behaves as a switchable shield that modulates the affinity of the helix for the axle. Reciprocally, the foldamer helix acts as a supramolecular auxiliary that compartmentalizes the axle. In some cases, the macrocycle is forced to move along the axle to allow the foldamer to reach its best recognition site.

Published
2021

50. (Trifluoromethylselenyl)methylchalcogenyl as Emerging Fluorinated Groups: Synthesis under Photoredox Catalysis and Determination of the Lipophilicity

Author

Kevin Grollier, Arnaud De Zordo-Banliat, Flavien Bourdreux, Guillaume Dagousset, Emmanuel Magnier, Thierry Billard, Bruce Pégot, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'Etude et de Recherche Multimodal Et Pluridisciplinaire en imagerie du vivant (CERMEP - imagerie du vivant), Université de Lyon-Université de Lyon-CHU Grenoble-Hospices Civils de Lyon (HCL)-CHU Saint-Etienne-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and ANR-18-CE07-0039,SAFA,Selenium et Fluor Associés: le mariage de 2 stars(2018)

Subjects
Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Decarboxylation, Organic Chemistry, Photoredox catalysis, chemistry.chemical_element, General Chemistry, Flow chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Lipophilicity, Fluorine, [CHIM]Chemical Sciences, Molecule, Surface modification, Oxidation-Reduction
Abstract

International audience; The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two-step strategy based on a metal-free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88% which raised to 98% in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physico-chemical characterization of these emerging groups was performed by determining their Hansch-Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95%. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives.

Published
2021

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