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1. New Janus Tricyclic Laddersiloxanes: Synthesis, Characterization, and Reactivity

Author

Yujia Liu, Midori Tokuda, Nobuhiro Takeda, Armelle Ouali, and Masafumi Unno

Subjects
tricyclic laddersiloxanes, Janus molecules, hydrosilylation, syn-type conformation, well-defined structures, Organic chemistry, QD241-441
Abstract

The synthesis of four novel syn-type tricyclic laddersiloxanes bearing eight or six alkenyl groups is presented. These compounds possess reactive alkenyl groups on both the bridged and side silicon atoms, and their structures were determined through characterization using multinuclear 1D and 2D NMR spectroscopy, mass spectrometry, and elemental analysis techniques. To investigate their reactivity, the compounds were subjected to hydrosilylation using two different silanes, and the resulting fully hydrosilylated compounds were thoroughly analyzed. Remarkably, all the synthesized laddersiloxanes displayed high thermal stability, suggesting their potential as promising precursors for the development of new hybrid materials. Additionally, preliminary findings indicate the possibility of exploiting the reactivity difference between the alkenyl groups attached to the D- and T-unit silicon atoms for the synthesis of Janus molecules. These findings highlight the potential of the reported compounds as valuable building blocks in the construction of innovative materials.

Published
2023
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2. Calcium-catalysed synthesis of amines through imine hydrosilylation: an experimental and theoretical study

Author

Yougourthen Boumekla, Fengjie Xia, Lucas Vidal, Cédric Totée, Christophe Raynaud, and Armelle Ouali

Subjects
Organic Chemistry, Physical and Theoretical Chemistry, Biochemistry
Abstract

Ca(NTf2)PF6, generated from commercial precursors, promotes imine hydrosilylation in high yields and is used to prepare a bioactive amine on the gram scale. The mechanistic investigations highlight an unprecedented Si–H activation by the Ca center.

Published
2023
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3. Grafting Copper Atoms and Nanoparticles on Double-Walled Carbon Nanotubes: Application to Catalytic Synthesis of Propargylamine

Author

David Mesguich, Lilian Moumaneix, Victor Henri, Morgan Legnani, Vincent Collière, Jérôme Esvan, Armelle Ouali, Pierre Fau, Centre National de la Recherche Scientifique - CNRS (FRANCE), Ecole Nationale Supérieure de Chimie de Montpellier - ENSCM (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), and Université de Montpellier (FRANCE)

Subjects
Metals, Matériaux, Carbon nanotubes, Electrochemistry, General Materials Science, Surfaces and Interfaces, Catalytic reactions, Functionalization, Condensed Matter Physics, Copper, Spectroscopy
Abstract

The decoration of carbon nanotubes (CNTs) by metal nanoparticles (NPs) combines the advantages of a high specific surface material with catalytic properties of metal nanocrystals. Little work has been devoted to the decoration of CNTs with copper NPs, and no evidence of copper atomic decoration of CNTs has shown up until now. Herein, we demonstrate that the strong acidic oxidation of double-walled CNTs (dwCNTs) is very efficient for the decoration of the carbon surface by copper NPs and atoms. This treatment severely degraded the CNT walls and generated a large amount of disordered sp3 carbon. This amorphous carbon film bears many chemically active functions like carboxyl and hydroxyl ones. In such conditions, the CNT walls behave as very efficient ligands for the stabilization of copper obtained by the thermolysis of the mesityl precursor in organic solution under mild dihydrogen pressure. In addition to copper NPs, we evidenced the presence of a regular coverage with copper atoms over the dwCNTs. This nanocomposite catalyzes the quantitative synthesis of propargylamines via one A3-type coupling reaction. Five consecutive catalytic cycles with 100% yield could be performed with no loss of activity, and the combination of Cu supported on dwCNTs allows a facile recycling of the catalytic material.

Published
2022
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7. Well-defined cyclic silanol derivatives

Author

Yujia Liu, Thanawat Chaiprasert, Armelle Ouali, and Masafumi Unno

Subjects
Inorganic Chemistry
Abstract

Cyclic silanol derivatives (CSDs), possessing siloxane rings consisting of T-unit silicon and oxygen atoms, are considered efficient precursors for the preparation of versatile well-defined building blocks of hybrid materials such as cyclic, cage- or ladder-type SQs. This review provides an outline of the main synthetic routes to numerous stereoregular CSDs with different sizes of siloxane rings since the first example of CSDs reported by Brown

Published
2022
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8. Synthesis and characterization of tetrathiol-substituted double-decker or ladder silsesquioxane nano-cores

Author

Armelle Ouali, Masafumi Unno, Nobuhiro Takeda, Yujia Liu, Mana Kigure, Riho Okawa, Gunma University, 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, biology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, 01 natural sciences, Silsesquioxane, 0104 chemical sciences, Characterization (materials science), Inorganic Chemistry, chemistry.chemical_compound, chemistry, Nano, Polymer chemistry, [CHIM]Chemical Sciences, Tetra, 0210 nano-technology, Double decker, ComputingMilieux_MISCELLANEOUS
Abstract

Tetra(3-mercaptopropyl)-silsesquioxanes with double-decker (DDSQ) or ladder nano-cores were easily prepared from the corresponding tetraallyl derivatives through fast and convenient thiol-ene reactions. An additional tetrathiol-DDSQ with more flexible arms was also synthesized in high yield from the corresponding tetrachloro-DDSQ derivative. The three novel tetrathiol silsesquioxanes described represent versatile building blocks for the preparation of hybrid organic-inorganic materials.

Published
2021
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9. Synthesis, Characterization, and Reaction of Divinyl‐substituted Laddersiloxanes

Author

Yujia Liu, Aimi Endo, Peiyao Zhang, Akira Takizawa, Nobuhiro Takeda, Armelle Ouali, Masafumi Unno, Gunma University, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), and Institute for Molecular & Cellular Regulation

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 02 engineering and technology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences, Electronic, Optical and Magnetic Materials
Abstract

International audience; superior properties. Among them, laddersiloxanes (ladder-type silsesquioxanes with defined structure) are less exploredbecause step-by-step synthesis is usually necessary. In order to investigate the properties of laddersiloxanes, and applythese compounds as monomer precursors to high function materials, we prepared laddersiloxanes with reactive vinylgroups.Methods The target compounds were obtained in a two-step reaction fromcommercially available alkoxysilanes, and total yieldswere 73–93 %. Three product stereoisomers were fully investigated by spectroscopic methods and structures were determined.Results As an extension of our previous research on constructing new laddersiloxanes, we will describe here the synthesis,characterization, and functionalization of novel divinyl-substituted laddersiloxanes. Further transformation of all productsproceeded smoothly, and extended laddersiloxanes were obtained by hydrosilylation. One isomer was isolated and the structurewas determined unequivocally by X-ray analysis.Conclusions The laddersiloxanes described here have two reactive vinyl groups at each end of the molecule. Various reactionsincluding hydrosilylation, polymerization, or olefin metathesis are possible, thus these compounds can be potential monomers forhighly functionalized materials.

Published
2021
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10. Synthesis, Characterization, and Reaction of Divinyl-Substituted Laddersiloxanes

Author

Armelle Ouali, Akira Takizawa, Peiyao Zhang, Yujia Liu, Nobuhiro Takeda, Masafumi Unno, and Aimi Endo

Subjects
010302 applied physics, Materials science, Olefin metathesis, Hydrosilylation, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Combinatorial chemistry, Characterization (materials science), chemistry.chemical_compound, Monomer, chemistry, Polymerization, 0103 physical sciences, Molecule, Surface modification, 0210 nano-technology
Abstract

Purpose Silsesquioxanes with well-defined structures have been of great interest recently because of their superior properties. Among them, laddersiloxanes (ladder-type silsesquioxanes with defined structure) were less explored because step-by-step synthesis is usually necessary. In order to investigate the properties of laddersiloxane, and apply these compounds to the monomers of high function materials, we prepared laddersiloxanes with reactive vinyl groups.MethodsThe target compounds were obtained in a two-step reaction from commercially available alkoxysilanes, and total yields were good. Three stereoisomers included in the products were fully investigated by spectroscopic methods and structures were determined. ResultsAs an extension of our previous research of constructing new laddersiloxanes, here we will describe the synthesis, characterization, and functionalization of novel divinyl-substituted laddersiloxanes. Further transformation of all products proceeded smoothly, and extended laddersiloxanes were obtained by hydrosilylation. One of the isomers was isolated and the structure was determined unequivocally by X-ray analysis. ConclusionThe laddersiloxanes described here have two reactive vinyl groups at each end of the molecule. Various reactions including hydrosilylation, polymerization, or olefin metathesis are possible, thus these compounds can be potential monomers for highly functionalized materials.

Published
2021
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11. Terpyridine–Ru Complexes Noncovalently Supported on Cobalt Magnetic Nanoparticles for Nitroarene Transfer Hydrogenation

Author

Olivier Dautel, Armelle Ouali, Houria Asri, 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, π-stacking interactions, 010405 organic chemistry, Magnetic nanoparticles (MNPs), chemistry.chemical_element, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Pyrene-tagged catalysts, chemistry.chemical_compound, Metrics & More Article Recommendations magnetic nanoparticles (MNPs), -stacking interactions, chemistry, nitroarene transfer hydrogenation, parasitic diseases, 2-propanol, Magnetic nanoparticles, [CHIM]Chemical Sciences, General Materials Science, Terpyridine, Cobalt
Abstract

International audience; This work reports the preparation and characterization of active and recyclable supported catalysts involving molecular Ru−terpyridine complexes and their ability to promote the transfer hydrogenation of nitroarenes in 2-propanol. The system proposed is based on the design of original pyrene-tagged terpyridine ligands, either monomeric "1 tpy " (one pyrene tag for one terpyridine) or multivalent "5 tpy " (one pyrene tag for five terpyridines), able to interact with the graphene surface of commercially available cobalt magnetic nanoparticles (MNPs) through π-stacking interactions. The existence of noncovalent interactions between the pyrene-tagged terpyridines and the MNP surface at 20°C was assessed by fluorescence spectroscopy for the first time in 2-propanol, an organic medium. Interestingly, 1 tpy and 5 tpy were shown to be released upon temperature increase (80°C) while the association was restored upon temperature decrease (20°C). The reversibility of this phenomenon enabled to reach high activities in nitroarene transfer hydrogenation for the corresponding Ru complexes (catalytic species are free in refluxing 2propanol) and high recyclabilities (noncovalent interactions are restored upon cooling). It is noteworthy that the multivalent ligand 5 tpy displaying, as expected, the higher terpyridine loading (0.15 mmol of tpy/g of MNPs vs 0.03 mmol for 1 tpy) also gave rise to the Ru catalyst with the best recyclability (8 consecutive cycles with no loss of activity against 5 cycles for the catalyst based on the monomeric ligand 1 tpy). In both cases, the ruthenium leaching was found to be low and the expected aniline met the requirements of the pharmaceutical industry (

Published
2020
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12. Conjugated Copolymers That Shouldn't Be

Author

Zejun Sun, Aimi Endo, Yujia Liu, John Kieffer, Siriporn Jungsuttiwong, Joseph C. Furgal, Nuttapon Yodsin, Masafumi Unno, Richard M. Laine, Daniel Hashemi, Ramin Ansari, Jun Guan, Shahrea Mahbub, Armelle Ouali, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), and Gunma University

Subjects
Biphenyl, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemistry, Polymer, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Medicine, Conjugated system, 010402 general chemistry, 01 natural sciences, Catalysis, Silsesquioxane, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Terphenyl, Siloxane, Polymer chemistry, Copolymer, Thiophene, ComputingMilieux_MISCELLANEOUS
Abstract

Multiple studies have explored using cage silsesquioxanes (SQs) as backbone elements in hybrid polymers motivated by their well-defined structures, physical and mechanical properties. As part of this general exploration, we reported unexpected photophysical properties of copolymers derived from divinyl double decker (DD) SQs, [vinyl(Me)Si(O 0.5 ) 2 ][PhSiO 1.5 ] 8 [(O 0.5 ) 2 Si(Me)vinyl] (vinylDDvinyl). These copolymers exhibit strong emission red-shifts from model compounds and implying unconventional conjugation, despite vinyl(Me)Si(O-) 2 siloxane bridges. In an effort to identify minimum SQ structures that do/do not offer extended conjugation; we explored Heck catalyzed co-polymerization of vinyl-ladder(LL)-vinyl compounds, vinyl(Me/Ph)Si(O 0.5 ) 2 [PhSiO 1.5 ] 4 (O 0.5 ) 2 Si(Me/Ph)vinyl, with Br-Ar-Br where Br-Ar-Br = 1,4-dibromobenzene, 4,4'-dibromo-1,1'-biphenyl, 4,4''-dibromo- p -terphenyl, 4,4'-dibromo- trans -stilbene, 2,7-dibromo-9,9-dimethyl-9H-fluorene, 2,5-dibromothiophene, 5,5'-dibromo-2,2'-bithiophene and 2,5-dibromo-thieno[3,2- b ]thiophene. Most surprising, the resulting oligomers show 30-60 nm emission red-shifts beyond those seen with vinylDDvinyl analogs despite lacking a true cage . Further evidence for unconventional conjugation includes apparent integer charge transfer (ICT) between LL-co-thiophene, bithiophene and thienothiophene with 10 mol% F 4 TCNQ, suggesting potential as p-type doped organic/inorganic semiconductors. Brominating DD/LL-co-phenyl polymer vinyl groups eliminates emission red-shifts. Zn debromination thereafter restores vinyl groups and emission red-shifts but brominated phenyls remain providing potential access to families of "hairy" conjugated SQ polymers.

Published
2020
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13. Styryl-Functionalized Cage Silsesquioxanes as Nanoblocks for 3-D Assembly

Author

Armelle Ouali, Carole Carcel, Mathilde Laird, John R. Bartlett, Masafumi Unno, Michel Wong Chi Man, Dan Dumitrescu, Arie van der Lee, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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 Européen des membranes (IEM), Université de Montpellier (UM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), University of the Sunshine Coast (USC), Gunma University, 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), Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), XRD2 beamline, Elettra - Sincrotrone Trieste S.C.p.A., Strada Statale 14- km 163,5 in AREA Science Park, 34149 Basovizza, Trieste, Italy, Western Sydney University, and Department of Chemistry and Chemical Biology, Graduate School of Science and Technology, Gunma University, Kiryu 376-8515, Gunma, Japan

Subjects
Silicon, Silsesquioxanes, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Crystal structure, Organic Chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Polymer chemistry, Moiety, Surface modification, Physical and Theoretical Chemistry, Cage, Functionalization, ComputingMilieux_MISCELLANEOUS, Vinyl
Abstract

International audience; Herein we report the synthesis of a new family of styryl-functionalized polyhedral oligomeric silsesquioxanes (Tn, where n = 8, 10, and 12), in which the organic moiety is linked to all n vertices of the Tn cages via the phenyl ring rather than the vinyl group. In contrast to earlier studies in which the styryl group is linked to the cage via the vinyl moiety, our approach ensures that the vinyl moiety is less sterically hindered and available for postfunctionalization. The functional Tn cages have been characterized by a range of techniques, including single crystal X-ray diffraction, multinuclear solution NMR (1H, 13C, and 29Si), MALDI-MS, and FTIR. The solid-state structure of the T8 compound exhibited two nonequivalent Si8O12 cage atoms, which has not been previously reported in the functionalized T8 system, although all cage atoms in the corresponding T10 and T12 systems were equivalent. In contrast, multinuclear solution NMR data indicated that all cages in the T8 system were equivalent in solution, suggesting that the nonequivalent cage geometries arise in the solid state to optimize the packing of the functionalized cages. These compounds have significant potential for future use in the production of 3D cross-linked polymer networks.

Published
2020
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15. π-Stacking Interactions of Graphene-Coated Cobalt Magnetic Nanoparticles with Pyrene-Tagged Dendritic Poly(Vinylidene Fluoride)

Author

Vincent Collière, Anne-Marie Caminade, Enrique Folgado, Marc Guerre, Christian Bijani, Kathleen I. Moineau-Chane Ching, Bruno Ameduri, Nidhal Mimouni, Vincent Ladmiral, Armelle Ouali, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
π-stacking, magnetic nanoparticles, Dendrimers, Materials science, Stacking, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Fluorescence spectroscopy, law.invention, chemistry.chemical_compound, law, Dendrimer, Moiety, Pyrenes, Graphene, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Poly(vinylidenefluoride), [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Pyrene, Magnetic nanoparticles, 0210 nano-technology, Cobalt
Abstract

International audience; This study investigates the non-covalent coating of cobalt magnetic nanoparticles (MNPs) involving a graphene surface with pyrene-tagged dendritic poly(vinylidene fluoride) (PVDF). Dendrimers bearing a pyrene moiety were selected to play the role of spacers between the graphene surface of the MNPs and the PVDF chains, the pyrene unit being expected to interact with the surface of the MNPs. The pyrene-tagged dendritic spacer 11 decorated with ten acetylenic units was prepared and fully characterized. Azido-functionalized PVDF chains were then grafted onto each branch of the dendrimer using Huisgen’s [3 + 2] cycloaddition reaction. Next, the association of the resulting pyrene-tagged dendritic PVDF 13 with commercially available Co/C MNPs by π -stacking interactions was studied by fluorescence spectroscopy. Evaluated were the stability of the π -stacking interactions when the temperature increased and the reversibility of the process when the temperature de- creased. Also, hybrid MNPs were prepared from pyrene-tagged dendrimers decorated either with acetylenic functions ( 11 ) or with PVDF branches ( 13 ), and they were characterized by transmission electron microscopy and comparative elemental analysis was carried out with naked MNPs.

Published
2018
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16. Heterogeneous Pd/POSS Nanocatalysts for C-C Cross-Coupling Reactions

Author

Preeyanuch Sangtrirutnugul, Armelle Ouali, Michel Wong Chi Man, Vuthichai Ervithayasuporn, Vetiga Somjit, Mahidol University [Bangkok], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), and Functional POSS as nanocatalysts

Subjects
Heterogeneous catalysis, Silsesquioxane, 010405 organic chemistry, Nanoparticle, chemistry.chemical_element, Silica, General Chemistry, 010402 general chemistry, 01 natural sciences, Nanomaterial-based catalyst, Coupling reaction, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Polymer chemistry, Nucleophilic substitution, [CHIM]Chemical Sciences, Palladium, POSS
Abstract

International audience; An insoluble solid support of N−heterocyclic imidazolium-functionalized cage-like silsesquioxane (SQ); Bim-SQ, was synthesized by nucleophilic substitution of octakis(3-chloropropyl)octasilsesquioxane with an excess bis-(imidazol-1-yl)methane and investigated as a new organic-inorganic hybrid support. In the presence of Bim-SQ, Pd(II) from [PdCl4]2− can be stabilized via both electrostatic interactions and imidazole-N-coordination, giving an amorphous material of Pd(II)@Bim-SQ. Subsequent in situ reduction of Pd(II)@Bim-SQ during Suzuki−Miyaura cross-coupling reactions afforded monodispersed Pd nanoparticles (2.33 ± 1.50 nm) stablized on Bim-SQ support, PdNp@Bim-SQ with Pd loading up to 14% w/w. Catalytic studies revealed that the pre-catalyst Pd(II)@Bim-SQ was active heterogeneous catalyst for Suzuki−Miyaura cross-coupling reactions, having the maximum TOFs of 5400 h−1 under mild conditions and in aqueous ethanol medium. Furthermore, PdNp@Bim-SQ was also shown to be an efficient catalyst for Heck reactions. Simple catalyst recovery and reusability of PdNp@Bim-SQ for at least 5 catalytic cycles without loss of activity were also demonstrated.

Published
2018
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17. The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects

Author

Daniel Duprez, Yves Schuurman, Françoise Maugé, Axel Löfberg, Pascal Fongarland, Franck Dumeignil, Christophe Geantet, Armelle Ouali, Helene Olivier-Bourbigou, Pascal Granger, Nathalie Tanchoux, Catherine Pinel, Anne-Cécile Roger, Denis Uzio, Céline Chizallet, François Jérôme, Pascale Massiani, Franck Launay, IFP Energies nouvelles (IFPEN), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Génie des Procédés Catalytiques (LGPC), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS), IRCELYON-C'Durable (CDURABLE), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), 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), IRCELYON-Catalyse Hétérogène pour la Transition Energétique (CATREN), Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-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), IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), 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 de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), 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), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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, École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), 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), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-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 d'Alsace (FMNGE), and 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)-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)

Subjects
Engineering, 010405 organic chemistry, business.industry, Organic Chemistry, Nanotechnology, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalysis, 0104 chemical sciences, Inorganic Chemistry, Engineering ethics, Physical and Theoretical Chemistry, business, ComputingMilieux_MISCELLANEOUS
Abstract

The review describes the most significant recent results achieved in France in the field of heterogeneous catalysis over the last 10 years. It focusses on the research carried out in the French academic laboratories, often in close collaboration with some industrial partners.

Published
2017
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18. Synthesis and Characterization of Functionalizable Silsesquioxanes with Ladder-type Structures

Author

Nobuhiro Takeda, Masafumi Unno, Yujia Liu, Armelle Ouali, Kazuki Onodera, Gunma University, 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
Inorganic Chemistry, chemistry.chemical_compound, 010405 organic chemistry, Chemistry, Hydrosilylation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Polymer chemistry, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Characterization (materials science)
Abstract

International audience; Novel tetravinyl-and tetraallyl-substituted laddersiloxanes were synthesized and characterized. It was shown that peripheral olefins could successfully undergo hydrosilylation quantitatively, possibly leading to tetrahalide ladder structures. All reported functional laddersiloxanes LS (LS-Vinyl4, LS-Allyl4, LS-Cl4 and LS-I4) thus constitute promising building blocks for more complex inorganic-organic hybrid materials.

Published
2019
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19. Synthesis, Characterization, and Functionalization of Tetrafunctional Double-Decker Siloxanes

Author

Yujia Liu, Nobuhiro Takeda, Masafumi Unno, Armelle Ouali, Gunma University, 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
010405 organic chemistry, Chemistry, Hydrosilylation, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Characterization (materials science), Inorganic Chemistry, chemistry.chemical_compound, Surface modification, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Hybrid material, Double decker
Abstract

International audience; Novel tetravinyl- and tetraallyl-substituted closed double-decker siloxanes (DDSQs) were synthesized and characterized, and their structures were elucidated by X-ray crystallographic analysis. Moreover, it was shown that peripheral olefins could successfully undergo hydrosilylation quantitatively. Such tetrafunctionalizable DDSQs (DDSQ-Vinyl4 and DDSQ-Allyl4) thus constitute promising building blocks for more complex inorganic–organic hybrid materials.SynopsisNovel tetravinyl- and tetraallyl-substituted closed double-decker siloxanes (DDSQs) were synthesized and peripheral olefins shown to successfully undergo hydrosilylation quantitatively. Such tetrafunctionalizable DDSQs thus constitute promising building blocks for more complex inorganic−organic hybrid materials.

Published
2019
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20. Cyclotriphosphazene, an old compound applied to the synthesis of smart dendrimers with tailored properties

Author

Armelle Ouali, Kathleen Moineau Chane-Ching, Cyrille Rebout, Jean-Pierre Majoral, Aurélien Hameau, Anne-Marie Caminade, Cédric-Olivier Turrin, Béatrice Delavaux-Nicot, Régis Laurent, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Dendrimers, ICPC-21, 010405 organic chemistry, Chemistry, General Chemical Engineering, Nanotechnology, General Chemistry, 010402 general chemistry, 01 natural sciences, Chemical synthesis, Phosphorus chemistry, 0104 chemical sciences, Dendrimer, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

The versatile reactivity of hexachlorocyclotriphosphazene (N3P3Cl6) has been developed for the synthesis of specifically engineered dendrimers. Dendrimers are hyperbranched macromolecules built by concentric layers constituted of associated monomeric units. Many of the properties of dendrimers depend on the type of their surface (terminal) functions, which are generally all identical. For some specific purposes, it is desirable to have one function that is different at the level of the core. Hexachlorocyclotriphosphazene offers the possibility to differentiate the reactivity of one (or more) Cl from the others, for producing specifically engineered dendritic tools. These specific reactions on N3P3Cl6 have produced highly dense dendrimers, Janus dendrimers (two faces), tools for functionalizing materials, with uses as catalysts, as chemical sensors, for trapping CO2, for the culture of cells, or for imaging biological events. These properties will be emphasized in this review.

Published
2016
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21. Cover Picture: The Pivotal Role of Catalysis in France: Selected Examples of Recent Advances and Future Prospects. (ChemCatChem 12/2017)

Author

Catherine Pinel, Yves Schuurman, Pascal Fongarland, Pascale Massiani, Axel Löfberg, Françoise Maugé, Armelle Ouali, Daniel Duprez, Franck Launay, Anne-Cécile Roger, Christophe Geantet, Franck Dumeignil, Denis Uzio, Helene Olivier-Bourbigou, Céline Chizallet, François Jérôme, Nathalie Tanchoux, Pascal Granger, IFP Energies nouvelles (IFPEN), Laboratoire de catalyse de Lille - UMR 8010 (LCL), Université de Lille, Sciences et Technologies-Centrale Lille-Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de recherches sur la catalyse (IRC), Centre National de la Recherche Scientifique (CNRS), Systèmes interfaciaux à l'echelle nanometrique (SIEN), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), 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, Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Hétérochimie Moléculaire et Macromoléculaire (HMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse (LMSPC), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-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 de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-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 Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Poitiers-Institut de Chimie du CNRS (INC), 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)-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), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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)-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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), 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), and Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Nanotechnology, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Inorganic Chemistry, Ab initio quantum chemistry methods, Cover (algebra), Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2017
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22. BF2 complexes of 1,3-diketones on the surface of phosphorus dendrimers: synthesis and study of the photoluminescence properties

Author

Aurélien Hameau, Anne-Marie Caminade, Mireille Blanchard-Desce, Olivier Mongin, Cédric Rouxel, Armelle Ouali, Jean-Pierre Majoral, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), 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), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Institut des Sciences Moléculaires (ISM), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Université Sciences et Technologies - Bordeaux 1-Université Montesquieu - Bordeaux 4-Institut de Chimie du CNRS (INC), CNRS, 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 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), Université de Toulouse (UT), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Diketone, Fluorophore, Photoluminescence, 010405 organic chemistry, Organic Chemistry, phosphorhydrazone, dioxaborine, General Chemistry, diketone, 010402 general chemistry, Photochemistry, 01 natural sciences, Fluorescence, Catalysis, 0104 chemical sciences, 3. Good health, dendrimers, chemistry.chemical_compound, Monomer, chemistry, Absorption band, Dendrimer, [CHIM]Chemical Sciences, Hypsochromic shift, fluorescence
Abstract

International audience; Difluoroboron complexes of monomeric and dimeric diketones and of generations 0-4 of phosphorus dendrimers ended by diketone ligands are synthesized and characterized. Their photoluminescence properties are measured. All compounds exhibit an intense absorption band in the near UV region. Both model dimers and dendrimers show a marked hypsochromic shift of this absorption band compared with the monomeric difluoroboron complex. The fluorescence of the dioxaborine complex subunit in the multichromophoric dendritic architectures is quenched compared with the emission of the isolated monomeric fluorophore, presumably due to interactions between the terminal groups of dendrimers.

Published
2017
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23. Catalysis Within Dendrimers

Author

Régis Laurent, Armelle Ouali, Anne-Marie Caminade, Jean-Pierre Majoral, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Poli, R.

Subjects
010405 organic chemistry, Chemistry, Asymmetric hydrogenation, Nanotechnology, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Covalent bond, Dendrimer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Catalytic efficiency, Metal nanoparticles, ComputingMilieux_MISCELLANEOUS, Macromolecule
Abstract

Dendrimers are hyperbranched macromolecules, synthesized step by step (generation after generation) in an iterative fashion, which structure is reminiscent to that of the branches of trees. Most of their properties are due to their terminal functions, which can be easily modified at will to fulfill the desired properties. In particular, many types of catalytic entities have been used as terminal groups of dendrimers. In some cases, a dendritic effect , that is the enhancement of the catalytic properties when a catalyst is linked to a dendrimer, has been observed. It is also generally possible to recover and reuse the dendritic catalysts. The internal structure of dendrimers can also play a key-role, as it manages cavities which can accommodate the catalytic entities, and enable the substrates to interact with them. Catalytic sites included inside the structure of dendrimers are rare, excepted if they constitute the core of dendrimers (or of dendrons, which are dendritic wedges). Effect of the confinement on the catalysis outcome is generally the main aim of these works. Another type of dendritic catalytic entities taking profit of the internal structure concerns metallic nanoparticles used as core of dendrimers. In this chapter, we will gather information about catalytic entities included inside dendrimers, either covalently linked, or noncovalently entrapped, and on their syntheses. The main types of reactions studied, the role of the generation (size) of the dendrimers, their recovery and reuse, and in general the effect of the confinement inside the dendritic structures on the catalytic efficiency will be discussed.

Published
2017
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24. Poly(phosphorhydrazone) metallodendrimers. A review

Author

Anne-Marie Caminade, Régis Laurent, Armelle Ouali, Jean-Pierre Majoral, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Chemistry, Nanoparticle, Nanotechnology, [CHIM.CATA]Chemical Sciences/Catalysis, Catalysis, Inorganic Chemistry, Transition metal, Dendrimer, Materials Chemistry, Surface modification, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Metal nanoparticles, ComputingMilieux_MISCELLANEOUS
Abstract

Poly(phosphorhydrazone) dendrimers constitute a versatile class of dendrimers, which can be functionalized at will at all levels of the structure (surface, core, branches) with various types of ligands (mono-, bi-, multi-dentate ligands), suitable for the complexation of different types of metals, including transition metals, lanthanides, or alkaline earths. This review is organized depending on the type of ligands. The properties of the corresponding complexes have been studied in many cases, and will be given. Most of the properties concern catalysis; a positive dendrimeric effect has been observed in many cases when the generation of the dendrimer increases. In many cases it is possible to recover the catalyst and to reuse it (up to ten times with the same efficiency). Other properties concern the field of materials, with the functionalization of the surface of electrodes, in particular with ferrocene-containing dendrimers, or the elaboration of metallic nanoparticles, and even their organization in dendritic networks. A single example of property in the field of biology is given, but it constitutes a promising result as anti-proliferative agents against cancerous cells.

Published
2014
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26. Grignard reagents and Copper

Author

Marc Taillefer and Armelle Ouali

Subjects
chemistry, 010405 organic chemistry, Reagent, General Physics and Astronomy, Organic chemistry, chemistry.chemical_element, General Materials Science, General Chemistry, 010402 general chemistry, 01 natural sciences, Copper, 0104 chemical sciences
Published
2016
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27. Well-defined poly(vinylidene fluoride) (PVDF) based-dendrimers synthesized by click chemistry: enhanced crystallinity of PVDF and increased hydrophobicity of PVDF films

Author

Marc Guerre, Bruno Ameduri, Armelle Ouali, Anne-Marie Caminade, Vincent Ladmiral, Christian Bijani, Enrique Folgado, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, 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, Polymers and Plastics, Organic Chemistry, Bioengineering, 02 engineering and technology, Fluorine-19 NMR, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, 0104 chemical sciences, Contact angle, chemistry.chemical_compound, Crystallinity, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Dendrimer, Polymer chemistry, Click chemistry, [CHIM]Chemical Sciences, Well-defined, 0210 nano-technology, High-resolution transmission electron microscopy, Fluoride, ComputingMilieux_MISCELLANEOUS
Abstract

This study reports the preparation by click chemistry of a novel fluorinated dendrimer bearing PVDF branches and its characterization by several analytical methods including 1H, 13C, 31P and 19F NMR, diffusional NMR, SEC, DLS, ATG, DSC and HRTEM. As remarkable properties, this dendritic PVDF displayed crystallinity (HRTEM highlighted crystalline disc-like zones of ca. 5 nm) and a much higher hydrophobicity than both its precursors with the water contact angle (WCA) reaching 108°.

Published
2016
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28. 6. Grignard reagents and Copper

Author

Armelle Ouali and Marc Taillefer

Subjects
chemistry.chemical_classification, chemistry, Reagent, chemistry.chemical_element, Organic chemistry, Copper, Catalysis, Coordination complex
Published
2016
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29. Coordination chemistry with phosphorus dendrimers. Applications as catalysts, for materials, and in biology

Author

Jean-Pierre Majoral, Anne-Marie Caminade, Cédric-Olivier Turrin, Régis Laurent, Armelle Ouali, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Nanotechnology, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, 0104 chemical sciences, Coordination complex, Catalysis, Inorganic Chemistry, chemistry, Homogeneous, Dendrimer, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Hybrid material, Metal nanoparticles, Macromolecule
Abstract

International audience; Dendrimers are hyperbranched macromolecules having a perfectly defined and multifunctionalized structure, constituted of branches emanating radially from a central core. The structure of dendrimers is particularly modular, and can incorporate in different parts coordination complexes. In this review, we will present the interplay between dendrimers and coordination chemistry in three main fields: catalysis, materials, and biology. Most of the examples will be taken from the work done with phosphorus-containing dendrimers, but the pioneering work carried out with other dendrimers will be also presented. One of the major improvements that metallodendrimers have afforded concerning catalysis is their easy recovery and reuse, bridging the gap between homogeneous and heterogeneous catalysis. Another major improvement concerns the “dendritic effect” which can afford impressive outcomes concerning the increase of yield and of enantioselectivity, together with a decrease of the leaching of metals, and consequently of waste. Dendrimers can be used also for the synthesis and stabilization of metallic nanoparticles, for the modification of metallic surfaces at the nanometric scale, and for the synthesis of mesoscopically ordered hybrid materials. Finally metallodendrimers have high potency against cancerous cell lines, and they appear to operate via a different mechanism of action compared with native metallodrugs, opening new avenues for the search of improved anti-cancer agents.

Published
2016
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30. Solventless synthesis of Ru(0) composites stabilized with polyphosphorhydrazone (PPH) dendrons and their use in catalysis

Author

Rocío Redón, Anne-Marie Caminade, Armelle Ouali, Nidia G. García-Peña, Cédric-Olivier Turrin, Departamento de Tecnociencias,Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, Universidad Nacional Autónoma de México (UNAM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, General Chemical Engineering, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Catalysis, Styrene, Sodium borohydride, chemistry.chemical_compound, chemistry, Dendrimer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 0210 nano-technology, Ruthenium chloride, Alkyl
Abstract

International audience; Ruthenium nanoparticles (NPs) are prepared by milling under air ruthenium chloride (RuCl3), sodium borohydride (NaBH4) and a polyphosphorhydrazone (PPH) dendron (generation 0 to 2) having an alkyl chain at the focal point and triarylphosphines on the surface. The resulting NPs have a diameter in the 2 to 3 nm range and they are stable upon storage in solution or as powders. They can efficiently catalyze hydrogenation of styrene. The interaction between the dendrons and the NPs is studied, and the influence of the alkyl chain length and dendron generation is also discussed.

Published
2016
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34. Phosphorus Dendrimers: Efficient Tools for 'Greener' Catalyst Design

Author

Armelle Ouali, Anne-Marie Caminade, Paul Servin, Laurie Travers, Jean-Pierre Majoral, Michel Keller, and Régis Laurent

Subjects
Inorganic Chemistry, Aqueous medium, Chemistry, Dendrimer, Organic Chemistry, Organic chemistry, Surface modification, Nanotechnology, Biochemistry, Large size, Catalysis
Abstract

The use of dendrimers as soluble supports of catalytic entities offers efficient tools for “greener” catalysis. Indeed, thanks to their large size, dendrimers can be recovered and reused; depending on their structure, they can be tolerant to aqueous media or even soluble in water; and they can be used as ligands of cheap metals such as copper. We describe several examples of dendritic catalysts having such properties, based on the functionalization of phosphorus-containing dendrimers.

Published
2011
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35. Phosphorus dendrimers as viewed by 31P NMR spectroscopy; synthesis and characterization

Author

Régis Laurent, Armelle Ouali, Cédric-Olivier Turrin, Anne-Marie Caminade, Béatrice Delavaux-Nicot, Cyrille Rebout, Maria Zablocka, and Jean-Pierre Majoral

Subjects
End-group, chemistry, General Chemical Engineering, Phosphorus, Dendrimer, Organic chemistry, chemistry.chemical_element, Phosphorus-31 NMR spectroscopy, General Chemistry, 31p nmr spectroscopy, Nuclear magnetic resonance spectroscopy, Combinatorial chemistry, Characterization (materials science)
Abstract

This review emphasizes the role of phosphorus for the elaboration of dendrimers and of various highly sophisticated dendritic structures, and the invaluable role played by 31P NMR for their characterization and to ascertain their purity. A few properties, highlighting the importance of phosphorus are reported at the end of this review.

Published
2010
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36. Nitrogen Ligands in Copper-Catalyzed Arylation of Phenols: Structure/Activity Relationships and Applications

Author

Armelle Ouali, Jean François Spindler, Marc Taillefer, Anny Jutand, Hétérochimie Moléculaire et Macromoléculaire (HMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Rhodia Organique Fine Centre de Recherches de Lyon (CRL), RHODIA, Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris)

Subjects
Denticity, 010405 organic chemistry, Ligand, Imine, Rational design, General Medicine, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Nucleophile, Pyridine, Organic chemistry, Chelation, Binding site, ComputingMilieux_MISCELLANEOUS
Abstract

In spite of the importance of ligand/ copper-catalyzed arylations of nucleophiles in organic chemistry, the structural and electronic features that make a ligand efficient in these reactions have not been determined until now. In this work, several bidentate ligands involving pyridine and/or imine nitrogen binding sites such as our lead ligand 1 have been synthesized, and tested in phenol arylations with a view to highlight relationships between the structure of the chelates and their efficacy. This study allowed us to more precisely define the role of each type of N-binding site during the catalytic process, and to discover new efficient ligands. Among them, the iminopyridine 6a, which is cheap and easy-to-prepare in high yield, is very attractive for industrial applications. Some examples of its field of application are presented here. In the future, the development of this work could allow a more rational design of efficient ligands in arylation reactions, without resorting to classical ligand screening.

Published
2007
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37. ChemInform Abstract: Phosphorus Dendrimers as Supports of Transition Metal Catalysts

Author

Anne-Marie Caminade, Régis Laurent, Armelle Ouali, and Jean-Pierre Majoral

Subjects
chemistry.chemical_compound, Monomer, chemistry, Organic reaction, Transition metal, Dendrimer, Phosphorus, Polymer chemistry, chemistry.chemical_element, General Medicine, Catalysis, Macromolecule
Abstract

Dendrimer are hyperbranched macromolecules, which can be used as support of catalytic entities. This review focusses on polyphosphorhydrazone (PPH) dendrimers, bearing as terminal groups, transition metal complexes of 3d elements (Cu, Sc) and 4d elements (Pd, Ru, Rh). These complexes have been used as catalysts for various organic reactions, in particular C–C couplings. Most of these dendritic complexes can be recovered and re-used several times (up to 12 successive runs with the same efficiency). In several cases, a dendritic (or dendrimer) effect is observed, i.e., an increased efficiency and/or enantioselectivity when comparing a monomeric catalyst with increasing generations of the dendrimers, using in all cases the same number of catalytic entities.

Published
2015
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38. The key role of the scaffold on the efficiency of dendrimer nanodrugs

Author

Armelle Ouali, Alexandrine Maraval, Cédric-Olivier Turrin, Anne-Marie Caminade, Rémy Poupot, Jean-Pierre Majoral, Valeri I. Kovalenko, Marek Maly, Matteo Garzoni, Mary Poupot, Giovanni M. Pavan, Séverine Fruchon, Victor Furer, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de Physiopathologie Toulouse Purpan (CPTP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches en Cancérologie de Toulouse (CRCT), Université Fédérale Toulouse Midi-Pyrénées, Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland, Scuola universitaria professionale della Svizzera italiana [Manno] (SUPSI), Kazan State Architect and Civil Engineering University, University of Kazan, A.E. Arbuzov Institute of Organic and Physical Chemistry (IOPC), Kazan Scientific Centre of the Russian Academy of Sciences, Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre de Physiopathologie Toulouse Purpan ex IFR 30 et IFR 150 (CPTP), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Gulli, Marie-Hélène, Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), and Scuola universitaria professionale della Svizzera italiana = University of Applied Sciences and Arts of Southern Switzerland [Manno] (SUPSI)

Subjects
Dendrimers, Scaffold, General Physics and Astronomy, Biocompatible Materials, Nanotechnology, 02 engineering and technology, Molecular Dynamics Simulation, Polypropylenes, 010402 general chemistry, 01 natural sciences, Monocytes, Article, General Biochemistry, Genetics and Molecular Biology, chemistry.chemical_compound, Molecular dynamics, Dendrimer, Humans, Polylysine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Aza Compounds, Multidisciplinary, Bone Density Conservation Agents, Diphosphonates, Molecular Structure, General Chemistry, Silanes, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Flow Cytometry, 021001 nanoscience & nanotechnology, Biocompatible material, 0104 chemical sciences, chemistry, Biophysics, Nanoparticles, 0210 nano-technology, Macromolecule
Abstract

Dendrimers are well-defined macromolecules whose highly branched structure is reminiscent of many natural structures, such as trees, dendritic cells, neurons or the networks of kidneys and lungs. Nature has privileged such branched structures for increasing the efficiency of exchanges with the external medium; thus, the whole structure is of pivotal importance for these natural networks. On the contrary, it is generally believed that the properties of dendrimers are essentially related to their terminal groups, and that the internal structure plays the minor role of an ‘innocent' scaffold. Here we show that such an assertion is misleading, using convergent information from biological data (human monocytes activation) and all-atom molecular dynamics simulations on seven families of dendrimers (13 compounds) that we have synthesized, possessing identical terminal groups, but different internal structures. This work demonstrates that the scaffold of nanodrugs strongly influences their properties, somewhat reminiscent of the backbone of proteins., The biological properties of dendrimers are thought to be largely dependent on the chemical nature of their surface. Here, the authors show that the internal scaffold of dendritic nanodrugs strongly influences their bioactivity, based on convergent information from biology and computation results.

Published
2015
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39. Phosphorus dendrimers as supports of transition metal catalysts

Author

Jean-Pierre Majoral, Armelle Ouali, Régis Laurent, Anne-Marie Caminade, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Phosphorus, chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Monomer, Organic reaction, chemistry, Transition metal, Dendrimer, Polymer chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Macromolecule
Abstract

International audience; Dendrimer are hyperbranched macromolecules, which can be used as support of catalytic entities. This review focusses on polyphosphorhydrazone (PPH) dendrimers, bearing as terminal groups, transition metal complexes of 3d elements (Cu, Sc) and 4d elements (Pd, Ru, Rh). These complexes have been used as catalysts for various organic reactions, in particular C–C couplings. Most of these dendritic complexes can be recovered and re-used several times (up to 12 successive runs with the same efficiency). In several cases, a dendritic (or dendrimer) effect is observed, i.e., an increased efficiency and/or enantioselectivity when comparing a monomeric catalyst with increasing generations of the dendrimers, using in all cases the same number of catalytic entities.

Published
2015
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40. The dendritic effect illustrated with phosphorus dendrimers

Author

Anne-Marie Caminade, Régis Laurent, Jean-Pierre Majoral, Cédric-Olivier Turrin, Armelle Ouali, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_compound, chemistry, 010405 organic chemistry, Dendrimer, Functional group, Polymer chemistry, Biophysics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences
Abstract

International audience; The dendritic (or dendrimer) effect is observed when a functional group behaves differently when it is alone or linked to a dendrimer; its properties can even vary depending on the generation of the dendrimers. The dendritic effect can be observed with any type of dendrimer, and for any type of property, even if it has been most generally tracked in catalysis and biology, and to a lesser extent in the field of materials. This review is mainly oriented towards the various types of dendritic effects observed with polyphosphorhydrazone dendrimers, even if many examples obtained with other types of dendrimers are given.

Published
2015
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41. Efficient and eco-compatible transition metal-free Oppenauer-type oxidation of alcohols

Author

Marc Taillefer, Anne-Marie Caminade, Jorge Ballester, Jean-Pierre Majoral, Armelle Ouali, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), 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), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ketone, Sodium, chemistry.chemical_element, Alcohol, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Transition metal, Oppenauer, Oxidation, Benzophenone, Organic chemistry, chemistry.chemical_classification, 010405 organic chemistry, Process Chemistry and Technology, Sodium tert-butoxide, General Chemistry, 0104 chemical sciences, chemistry, Alcohol oxidation, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract

International audience; Catalytic amounts of cheap, non-toxic, easy-to-handle and non-sensitive sodium tert-butoxide are able to promote the dehydrogenative oxidation of a wide array of secondary alcohols using inexpensive benzophenone as the H-acceptor. The corresponding ketones, highly important intermediates and targets throughout life and material sciences, are very selectively obtained under mild conditions

Published
2014
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42. Efficient Iron/Copper Co-Catalyzed Arylation of Nitrogen Nucleophiles

Author

Ning Xia, Marc Taillefer, and Armelle Ouali

Subjects
Alkylation, Nitrogen, Iron, chemistry.chemical_element, Halide, 010402 general chemistry, Hydrocarbons, Aromatic, 01 natural sciences, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Nucleophile, Polymer chemistry, Organic chemistry, Bimetallic strip, Iron copper, Molecular Structure, 010405 organic chemistry, Aryl, Stereoisomerism, General Medicine, General Chemistry, Copper, 0104 chemical sciences, 3. Good health, chemistry
Abstract

In summary, we have presented here a first and original example of a cooperative bimetallic catalysis [Fe]-[Cu] allowing the N-arylation of various nitrogen nucleophiles from differently substituted aryl halides (X = I, Br, Cl)

Published
2007
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43. ChemInform Abstract: Dendrimers or Nanoparticles as Supports for the Design of Efficient and Recoverable Organocatalysts?

Author

Oliver Reiser, Arnaud Perrier, Anne-Marie Caminade, Sebastian Wittmann, Jean-Pierre Majoral, Armelle Ouali, Michel Keller, Laurie Travers, and Roland Linhardt

Subjects
chemistry.chemical_compound, Addition reaction, surgical procedures, operative, chemistry, Trimethylsilyl, Dendrimer, Organocatalysis, Nanoparticle, Ether, General Medicine, Combinatorial chemistry
Abstract

Dendrimers grafted with (S)-α,α-diphenylproline trimethylsilyl ether moieties are presented as organocatalysts.

Published
2013
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44. ChemInform Abstract: An Efficient and Recyclable Dendritic Catalyst Able to Dramatically Decrease Palladium Leaching in Suzuki Couplings

Author

Sonia Ladeira, Michel Keller, Anne-Marie Caminade, Jean-Pierre Majoral, Aurélien Hameau, Armelle Ouali, and Grégory Spataro

Subjects
chemistry.chemical_compound, Monomer, chemistry, Inorganic chemistry, chemistry.chemical_element, macromolecular substances, General Medicine, Leaching (metallurgy), Catalysis, Palladium
Abstract

A series of novel monomeric and dentritic thiazolyl phosphines is prepared and their activity in Suzuki couplings evaluated.

Published
2013
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45. Pyrene-tagged dendritic catalysts noncovalently grafted onto magnetic Co/C nanoparticles: an efficient and recyclable system for drug synthesis

Author

Anne-Marie Caminade, Oliver Reiser, Michel Keller, Armelle Ouali, Jean-Pierre Majoral, Vincent Collière, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universität Regensburg (UR)

Subjects
magnetic nanoparticles, Phosphines, Nanoparticle, 010402 general chemistry, 01 natural sciences, Catalysis, dendrimers, chemistry.chemical_compound, Polymer chemistry, Recycling, Magnetite Nanoparticles, catalyst recycling, Pyrenes, 010405 organic chemistry, General Chemistry, Cobalt, General Medicine, palladium, Carbon, 0104 chemical sciences, 3. Good health, Drug synthesis, chemistry, Chemical engineering, Pharmaceutical Preparations, Pyrene, Suzuki coupling
Abstract

1521-3773

Published
2013
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46. Efficient and recyclable rare earth-based catalysts for Friedel–Crafts acylations under microwave heating: dendrimers show the way

Author

Jean-Pierre Majoral, Arnaud Perrier, Michel Keller, Anne-Marie Caminade, Armelle Ouali, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
010405 organic chemistry, Chemistry, Ligand, Rare earth, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Pollution, 0104 chemical sciences, Catalysis, Acylation, chemistry.chemical_compound, Microwave heating, Dendrimer, Environmental Chemistry, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Terpyridine, Friedel–Crafts reaction
Abstract

International audience; The catalytic system involving Sc(OTf )3 and a dendritic terpyridine ligand is able to promote the Friedel–Crafts acylation of a wide range of aromatics under microwave irradiation. The expected products are obtained in high yields after short reaction times and the nano-sized catalyst can be recovered and successfully used in 12 consecutive runs.

Published
2013
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47. Dendrimers : Towards Catalytic, Material and Biomedical Uses

Author

Anne-Marie Caminade, Cedric-Olivier Turrin, Regis Laurent, Armelle Ouali, Beatrice Delavaux-Nicot, Anne-Marie Caminade, Cedric-Olivier Turrin, Regis Laurent, Armelle Ouali, and Beatrice Delavaux-Nicot

Subjects
Dendrimers
Abstract

This book will be mainly focussed on the properties and uses of dendrimers and dendrons. The aim of this book is to be the reference book about dendrimers applications. It will not describe all details, but it will give the reader a unique overview of what has currently been done with dendrimers, with numerous references and illustrations. It will be divided in four main parts: Part 1) Generalities, syntheses, characterizations and properties; Part 2) Applications in catalysis; Part 3) Applications for the elaboration or modification of materials; and Part 4) Applications in biology/medicine. The role of the nanometric size and the multiple functions of dendrimers on the properties will be emphasized.

Published
2011

48. ChemInform Abstract: Organocatalysis with Dendrimers

Author

Armelle Ouali, Michel Keller, Anne-Marie Caminade, and Jean-Pierre Majoral

Subjects
Metal, Chemistry, Dendrimer, visual_art, Organocatalysis, visual_art.visual_art_medium, General Medicine, Bond formation, Combinatorial chemistry, Bond cleavage, Large size, Catalysis
Abstract

This review gives an overview of the use of dendrimers and dendrons as organocatalysts, i.e. as catalysts in the absence of any metal. A large variety of dendrimeric structures have already been used for such a purpose, varying in size (generation), type and location (core or surface) of the organocatalytic entities, and overall chemical composition. The main types of reactions catalyzed concern bond formation (in particular C–C bonds), bond cleavage (in particular of esters), reductions and oxidations. In many cases, good to excellent enantioselectivities have been observed, in some cases associated with a positive dendritic effect (better properties when the generation of the dendrimer increases). Due to their large size compared to products, the dendrimeric organocatalysts can be often recovered and reused several times.

Published
2012
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49. Organocatalysis with dendrimers

Author

Jean-Pierre Majoral, Anne-Marie Caminade, Armelle Ouali, Michel Keller, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Aldehydes, Dendrimers, Esterification, 010405 organic chemistry, Chemistry, General Chemistry, Bond formation, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Metal, Metals, visual_art, Dendrimer, Organocatalysis, visual_art.visual_art_medium, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Oxidation-Reduction, Large size, Bond cleavage
Abstract

International audience; This review gives an overview of the use of dendrimers and dendrons as organocatalysts, i.e. as catalysts in the absence of any metal. A large variety of dendrimeric structures have already been used for such a purpose, varying in size (generation), type and location (core or surface) of the organocatalytic entities, and overall chemical composition. The main types of reactions catalyzed concern bond formation (in particular C–C bonds), bond cleavage (in particular of esters), reductions and oxidations. In many cases, good to excellent enantioselectivities have been observed, in some cases associated with a positive dendritic effect (better properties when the generation of the dendrimer increases). Due to their large size compared to products, the dendrimeric organocatalysts can be often recovered and reused several times.

Published
2012
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50. Synthesis of Dendritic β-Diketones and Their Application in Copper-Catalyzed Diaryl Ether Formation

Author

Mykhailo Ianchuk, Marc Taillefer, Sonia Ladeira, Jean-Pierre Majoral, Anne-Marie Caminade, Armelle Ouali, Michel Keller, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, 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
Dendrimers, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Phenols, Dendrimer, Polymer chemistry, Organic chemistry, Physical and Theoretical Chemistry, Diketone ligands, Diketone, 010405 organic chemistry, Ligand, Aryl, Organic Chemistry, Phosphorus, Arylation, Copper, 0104 chemical sciences, Monomer, chemistry, [CHIM.CHEM]Chemical Sciences/Cheminformatics, Macromolecule
Abstract

International audience; Phosphorus-based dendrimers decorated with β-diketones were prepared and fully characterized. These macromolecules, which are the first examples of multivalent dendrimeric β-diketones, were tested as ligands for copper in O-arylations of 3,5-dimethylphenol by aryl bromides. Although no dendrimer effect was observed, we were able to highlight a very efficient catalytic system that involved a monomeric β-diketone as the ligand. The proposed conditions are very competitive in terms of catalyst and base loading as the C-O coupling can be efficiently performed by using low amounts of copper precursor (1 mol-% instead of 5-10 mol-%), diketone (4 mol-% instead of 25-80 mol-%), and base (1.2 equiv. of cesium carbonate instead of 2 or more). Moreover, the absence of the dendrimer effect is explained by the decomposition of the dendrimer under the reaction conditions, which led to the release of the peripheral diketone moieties.

Published
2012
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