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51 results on '"Salt metathesis reaction"'

1. Studies on The Application of The Paternò‐Büchi Reaction to The Synthesis of Novel Fluorinated Scaffolds

Author

Corentin Lefebvre, Jean-Pierre Vors, Alexander Sudau, Norbert Hoffmann, Pierre Genix, Mario Andrés Gomez Fernandez, Manabu Abe, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), and Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Reaction mechanism, Ketone, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Regioselectivity, Stereoisomerism, Context (language use), General Chemistry, Alkenes, Ketones, 010402 general chemistry, Oxetane, 01 natural sciences, Catalysis, Paternò–Büchi reaction, Cycloaddition, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Salt metathesis reaction, Organic chemistry
Abstract

International audience; In the context of new scaffolds obtained by photochemical reactions, Paternò-Büchi reactions between heteroaromatic, trifluoromethylphenyl ketone and electron rich alkenes to give oxetanes are described. A comprehensive study has then been carried out on the reaction of aromatic ketones with fluorinated alkenes. Depending on the substitution pattern at the oxetane ring, a metathesis reaction is described as a minor side process to give mono fluorinated alkenes. Overall, this last reaction corresponds to a photo-Wittig reactions and yield amid isosteres. In order to explain the uncommon regioselectivity of the Paternò-Büchi reaction with these alkenes, electrostatic-potential derived charges (ESP) have been determined. In a second computational study, the relative stabilities of the typical 1,4-diradical intermediates of the Paternò-Büchi reaction have been determined. The results well explain the regioselectivity. Further transformations of the oxetanes or previous functionalization of the fluoroalkenes open perspectives for oxetanes as core structures for biologically active compounds.

Published
2021

2. Bacterial nanocellulose membranes loaded with vitamin B-based ionic liquids for dermal care applications

Author

Mukesh Sharma, Véronique Coma, and Armando J. D. Silvestre, Eduardo M. Costa, Guillaume Chantereau, Mariana Veiga, Carmen S. R. Freire, F. Antunes, Mara G. Freire, Atiye Abednejad, Carla Vilela, M. M. Pintado, Gilles Sèbe, Centre de Recherche des Cordeliers (CRC), Université Pierre et Marie Curie - Paris 6 (UPMC)-École pratique des hautes études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centro de Investigacao em Materiais Ceramicaos e Compositos (CICECO), Universidade de Aveiro, Université Paris Diderot - Paris 7 (UPD7)-École pratique des hautes études (EPHE)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Descartes - Paris 5 (UPD5)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), TEAM 2 LCPO, Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), and Veritati - Repositório Institucional da Universidade Católica Portuguesa

Subjects
Skin care applications, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Nanocellulose, chemistry.chemical_compound, Antioxidant activity, Materials Chemistry, Salt metathesis reaction, Organic chemistry, Physical and Theoretical Chemistry, Solubility, Thermal analysis, Vitamin B, Spectroscopy, ComputingMilieux_MISCELLANEOUS, Chemistry, Plasticizer, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Cholinium-based ILs, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Bioavailability, Ionic liquids, Membrane, [CHIM.POLY]Chemical Sciences/Polymers, Bacterial nanocellulose, Ionic liquid, 0210 nano-technology
Abstract

The development of innovative bio-based skin care products has received an increased attention in the latter years. In the present work, the synthesis of original active principle ingredients based on ionic liquids (ILs) with cholinium cation and vitamins B anions, followed by their incorporation in bacterial nanocellulose (BC) membranes for topical applications, is reported. Three ILs, namely cholinium nicotinate [Ch][B3], cholinium pantothenate [Ch][B5] and cholinium pyridoxylate [Ch][B6], were synthesized through a metathesis reaction and their structure characterized in detail. Thermal analysis confirmed their denomination as ILs and their high thermal resistance. The solubility of these ILs was higher than their vitamin precursors, especially in the case of [Ch][B3] whose solubility increased 30.6-fold enhancing the bioavailability of this vitamin. The incorporation of ILs in BC led to translucent and homogeneous membranes stable up to 190 °C. ILs acted as plasticizers reducing BC brittleness that facilitated their application on irregular skin regions. Moreover, the re-hydration ability of BC-ILs membranes was improved 2.9 to 4.8-fold in comparison to BC, ensuring adequate hydration for ILs release, while the release of ILs in buffer solutions was more complete and faster than the release of vitamins. Finally, BC-ILs were proven not cytotoxic to skin epithelial cells and thus are suitable materials for skin care applications.

Published
2020

3. New Robust Luminescent Supramolecular Assemblies Based on [Ln(Mo 8 O 26 ) 2 ] 5– (Ln = Eu, Sm) Polyoxometalates

Author

Bernard Humbert, Hélène Serier-Brault, Thibault Amiaud, Eric Faulques, Nicolas Albrecht, Patricia Bolle, Rémi Dessapt, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), and Université de Nantes (UN)-Université de Nantes (UN)

Subjects
chemistry.chemical_classification, Photoluminescence, 010405 organic chemistry, Supramolecular chemistry, Salt (chemistry), Phosphor, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Salt metathesis reaction, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical chemistry, Thermal stability, Physical and Theoretical Chemistry, Luminescence, Acetonitrile, ComputingMilieux_MISCELLANEOUS
Abstract

This work highlights for the first time the photoluminescence (PL) properties of two new [Ln(Mo8O26)2]5- (Ln = Eu, Sm) lanthanide-containing polyoxometalates. Stable crystals of their tetrabutylammonium salts were synthesized, and their structures were confirmed by single-crystal X-ray diffraction. The robustness of the [Ln(Mo8O26)2]5- complexes in an acetonitrile solution has been evidenced by Fourier transform Raman and PL spectroscopies. The tetraphenylphosphonium derivatives were obtained by a salt metathesis reaction. The two series exhibit high thermal stability in air and are efficient phosphors at room temperature.

Published
2019

4. α,ω-Di(vinylene carbonate) telechelic polyolefins: Synthesis by metathesis reactions and studies as potential precursors toward hydroxy-oxazolidone-based polyolefin NIPUs

Author

Guillaume Michaud, Cyril Chauveau, Frédéric Simon, Stéphane Fouquay, Sophie M. Guillaume, Jean-François Carpentier, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Bostik Smart Technology Centre (BOSTIK), Arkema (Arkema), Bostik, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Polymers and Plastics, General Physics and Astronomy, Metathesis, 02 engineering and technology, Oxazolidone, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Telechelic polyolefin, Polymer chemistry, Materials Chemistry, Salt metathesis reaction, [CHIM]Chemical Sciences, Reactivity (chemistry), Hydroxymethyl, Vinylene carbonate, Methyl acrylate, Ethylenedioxy, Chemistry, Organic Chemistry, ROMP, 021001 nanoscience & nanotechnology, Non-isocyanate polyurethane (NIPU), 0104 chemical sciences, 0210 nano-technology
Abstract

International audience; Current polyurethane (PU) industrial and academic research aims at developing non-isocyanate PUs, referred to as NIPUs. Within this context, we report herein the synthesis of original vinylene carbonate (VC) compounds, subsequently used as chain-transfer agents (CTAs) towards the preparation of α,ω-di(VC) telechelic (co)polyolefins from the tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins. Thus, (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl acrylate (VC1), bis((5-methyl-2-oxo-1,3-dioxol-4-yl)methyl) fumarate (VC2), and bis((5-methyl-2-oxo-1,3-dioxol-4-yl)methyl) (E)-hex-3-enedioate (VC3) were synthesized from 4-(hydroxymethyl)-5-methyl-1,3-dioxol-2-one (DMDO-OH). Among these, only VC3 successfully and selectively afforded well-defined α,ω-di(vinylene carbonate) telechelic polyolefins, namely di(VC3)-PCOE and di(VC3)-P(NB-co-CDT), from the ROMP/CM of COE, and norbonene (NB)/trans,trans,cis-1,5,9-cyclododecatriene (CDT), respectively, using Grubbs’ 2nd-generation ruthenium catalyst (G2) under mild operating conditions (CH2Cl2, 40 °C, 3 h). Preliminary investigations on the reactivity of a model VC, namely 4,5-dimethyl-1,3-dioxol-2-one (DMDO), towards nucleophiles such as a primary or secondary amine, promisingly showed the formation of hydroxy-oxazolidone compounds 1 and 2, and oxo-urethane 3 species, respectively. Yet, the ultimate reaction of di(VC3)-PCOE with 2,2′-(ethylenedioxy)bis(ethylamine) (EDR-148) did not give the expected poly(di(hydroxy-oxazolidone)polyolefin) polyaddition type of NIPUs; competing amidation and/or dehydration or urea formation reactions evidenced by detailed NMR, FTIR and MS analyses, were proposed to account for this inefficiency.

Published
2019

5. Reversible ionically-crosslinked single chain nanoparticles as bioinspired and recyclable nanoreactors for N -heterocyclic carbene organocatalysis

Author

Rachel K. O'Reilly, Sofiem Garmendia, Daniel Taton, Andrew P. Dove, Laboratoire de Chimie des Polymères Organiques (LCPO), Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Team 1 LCPO : Polymerization Catalyses & Engineering, Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Birmingham [Birmingham], The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no. 642671, project 'SUSPOL-EJD'., European Project: 642671,H2020,H2020-MSCA-ITN-2014,SUSPOL(2015), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)

Subjects
Polymers and Plastics, Organic Chemistry, Bioengineering, Chain transfer, 02 engineering and technology, Nanoreactor, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, Monomer, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Benzoin, Organocatalysis, Amphiphile, Ionic liquid, Salt metathesis reaction, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract

International audience; The intrinsic advantages of poly(ionic liquid)s (PILs), based on their high chemical activity and flexible structure, have been harnessed by exploring their applicability as catalytic single chain nanoparticles (SCNPs). A non-covalent bioinspired approach has been established to ionically crosslink an imidazolium-based poly(ionic liquid) to form folded SCNPs. An amphiphilic styrenic-type coPIL was synthesized by reversible addition fragmentation chain transfer (RAFT) to include hydrophilic stabilizer units, hydrophobic spacers and two antagonist functionalities randomly distributed through the polymer backbone. The antagonist functionalities were then intramolecularly and ionically crosslinked using a simple anion metathesis reaction, which resulted in folding to form the SCNPs under mild conditions. The folding process enabled the protection of the N-heterocyclic carbene (NHC) functionality, through the benzoate–imidazolium interaction between antagonist monomer units. Upon the application of heat, free NHCs could be generated within the confined SCNPs, which could be further utilized in benzoin catalysis. Most importantly, the reversible nature of the crosslinking and reversible generation of the active functionality allowed for the utilization of the SCNPs as a recyclable catalytic support.

Published
2018

6. Synthesis, structure and magnetic properties of the dinuclear complex [1,3-C6H4{NC(Ph)N(SiMe3)}2]3Dy2 coordinated by ansa-bis(amidinate) ligands with a m-phenylene linker

Author

Alexander A. Trifonov, Jérôme Long, Anton V. Cherkasov, Joulia Larionova, Grigory G. Skvortsov, Russian Acad Sci, GA Razunaev Inst Organomet Chem, Russian Academy of Sciences [Moscow] (RAS), 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 G. A. Razuvaev Institute of Organometallic Chemistry

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Salt (chemistry), General Chemistry, Atmospheric temperature range, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, Crystallography, Phenylene, Reagent, Salt metathesis reaction, Anhydrous, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Linker, ComputingMilieux_MISCELLANEOUS
Abstract

A salt metathesis reaction of anhydrous DyCl3 and [1,3-C6H4{NC(Ph)N(SiMe3)}2Li2(THF)2] in THF affords the complex [1,3-C6H4{NC(Ph)N(SiMe3)}2]3Dy2 regardless of a ratio between reagents. The assembling of a binuclear core results from a spanning coordination of the amidinate fragments of three μ-bridging ansa-bis(amidinate) ligands to two Dy3+ ions. The magnetic properties of the product were studied by SQUID magnetometry in a temperature range of 1.8–300 K.

Published
2018

7. Synthesis and Application of Stereoretentive Ruthenium Catalysts on the Basis of the M7 and the Ru-Benzylidene-Oxazinone Design

Author

Idriss Curbet, Adrien Dumas, Olivier Baslé, Loïc Toupet, Marc Mauduit, Daniel S. Müller, Mathieu Rouen, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), CNRS, Ecole Nationale Superieure de Chimie de Rennes, ANRT, Demeta SAS (CIFRE) [2014/0702], FASO, region Bretagne [9639], 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 de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], 010405 organic chemistry, Ligand, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Ruthenium, Inorganic Chemistry, chemistry, Salt metathesis reaction, Reactivity (chemistry), Physical and Theoretical Chemistry
Abstract

International audience; A series of new stereoretentive ruthenium catalysts bearing the dithiocatecholate ligand was synthesiszed on the basis of the M7 and Ru-benzylidene-oxazinone design. The activity of the catalysts was tested in ring-opening cross-metathesis reactions, ring-closing metathesis reactions, cross-metathesis reactions, and self-metathesis reactions using Z- and E-configured starting materials. The desired metathesis products were obtained with moderate to high yields and with excellent stereoselectivities (>95%). Substrate-dependent reactivity was found by carrying out kinetic studies on internal and terminal olefins.

Published
2018

8. Synthesis, APPI Mass-Spectrometric Characterization, and Polymerization Studies of Group 4 Dinuclear Bis(ansa-metallocene) Complexes

Author

Alexandre Welle, Gilles Schnee, Jean-Michel Brusson, Jean-François Carpentier, Pierre Giusti, Aurélien Vantomme, Evgueni Kirillov, Leslie Bitard, Mathilde Farenc, Carlos Afonso, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Total Petrochemicals Feluy, TOTAL FINA ELF, TOTAL SA, Total S.A., Total Research and Technologies Feluy, Total Research and Technologies Gonfreville, 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), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nucleophilic addition, Ethylene, Ligand, metallocene catalysts, mass-spectroscopy, [CHIM.CATA]Chemical Sciences/Catalysis, lcsh:Chemical technology, Medicinal chemistry, 3. Good health, Catalysis, lcsh:Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, lcsh:QD1-999, chemistry, Polymerization, Salt metathesis reaction, Copolymer, lcsh:TP1-1185, Ansa-metallocene, [CHIM.COOR]Chemical Sciences/Coordination chemistry, olefin polymerization, inorganic_nuclear_chemistry
Abstract

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b), meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a&ndash, c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2), m-, R = Me (3c-Zr2), were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and a greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

Published
2018

9. Ring-closing metathesis of fluoroalkenes toward the synthesis of fluorinated heterocycles containing an oxaza bond

Author

Xavier Pannecoucke, Annie-Claude Gaumont, David Guerin, Isabelle Dez, Samuel Couve-Bonnaire, Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Double bond, Olefin metathesis, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Side reaction, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Ring-closing metathesis, chemistry, Salt metathesis reaction, Organic chemistry, Moiety
Abstract

International audience; This study reports the ring-closing metathesis reaction of bisolefins, including a reluctant fluoroalkenes, linked with oxaza moiety. The resulting heterocycles were produced in high yields under high diluting conditions disfavoring the homodimerization side reaction of nonfluorinated double bond. The use of a mixture of solvents proved to be a good strategy to obtain the fluorinated heterocycles in fair to excellent yields.

Published
2018

10. Study of the Cross-Metathesis Reaction of α-Hydroxy β,γ-Unsaturated Amides towards a Rapid and Flexible Total ­Synthesis of Symbioramide and its Isomer

Author

Alexandre Gratais, Samir Bouzbouz, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cross-metathesis, 010405 organic chemistry, Stereochemistry, Chemistry, Organic Chemistry, Total synthesis, Symbioramide, Hydroxyamide, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, γ-silyl butenamides, Synthesis, Salt metathesis reaction, [CHIM]Chemical Sciences, Reactivity (chemistry), Serine methyl ester
Abstract

International audience; The reactivity of novel α-hydroxy β,γ-unsaturated amides in cross-metathesis reactions was extensively studied and used to perform a short total synthesis of symbioramide and its isomer from ­l-serine methyl ester.

Published
2018

11. Iron(III) Pincer Complexes as a Strategy for Anticancer Studies

Author

Alexander D. Ryabov, Alexandre Gries, Christian Gaiddon, Ronan Le Lagadec, Aldo S. Estrada-Montaño, Gaiddon, Christian, Instituto de Química [México, Mexico], Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM)-Ciudad Universitaria, Department of Chemistry [Pittsburgh, PA, USA], Carnegie Mellon University [Pittsburgh] (CMU), Equipe 2 'Réponse au Stress Cellulaire & Thérapies Innovantes' / 'Stress Response & Innovative Therapies' (STREINTH - Inserm U1113), Interface de Recherche Fondamentale et Appliquée en Cancérologie (IRFAC - Inserm U1113), Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre Paul Strauss : Centre Régional de Lutte contre le Cancer (CRLCC)-Fédération de Médecine Translationelle de Strasbourg (FMTS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre Paul Strauss : Centre Régional de Lutte contre le Cancer (CRLCC)-Fédération de Médecine Translationelle de Strasbourg (FMTS), Service d'oncologie médicale [CHU Strasbourg], CHU Strasbourg, Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre Paul Strauss : Centre Régional de Lutte contre le Cancer (CRLCC)-Fédération de Médecine Translationelle de Strasbourg (FMTS), We are thankful for financial support from the Consejo Nacional de Ciencia y Tecnología (Project 153151) and the Dirección General de Asuntos del Personal Académico (DGAPA) (PAPIIT project IN-207316 and postdoctoral grant to A. S. E.-M.)., and Ciudad Universitaria-Universidad Nacional Autónoma de México (UNAM)

Subjects
Stereochemistry, Cytotoxicity, Iron, [SDV]Life Sciences [q-bio], [SDV.CAN]Life Sciences [q-bio]/Cancer, [SDV.BC]Life Sciences [q-bio]/Cellular Biology, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Pincer ligands, Inorganic Chemistry, chemistry.chemical_compound, Transmetalation, [SDV.CAN] Life Sciences [q-bio]/Cancer, medicine, Salt metathesis reaction, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, Benzene, Pincer ligand, [SDV.BC] Life Sciences [q-bio]/Cellular Biology, Cisplatin, Antitumor agents, 010405 organic chemistry, Chemistry, Structure elucidation, Cancer, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, medicine.disease, 0104 chemical sciences, 3. Good health, Pincer movement, [SDV] Life Sciences [q-bio], [SDV.SP] Life Sciences [q-bio]/Pharmaceutical sciences, Cyclic voltammetry, medicine.drug
Abstract

International audience; [Fe(NCN)2]PF6 (1·PF6) [NCHN = 1,3-di(pyridin-2-yl)benzene] was readily obtained by a transmetalation reaction between [Fe3(CO)12] and Hg(NCN)Cl followed by a metathesis reaction with KPF6. X-ray diffraction, electron paramagnetic resonance spectroscopy, and cyclic voltammetry studies confirmed the proposed structure. Cytotoxic assays in human colon cancer (HCT-15), lung cancer (SKLU), and gastric cancer (AGS, KATOIII) cells were performed, and the IC50 data obtained for all cell lines showed that 1·PF6 has a much higher activity than cisplatin.

Published
2017

12. New route to carbonate-functionalized imidazolium and pyrrolidinium-based ionic liquids

Author

Catherine C. Santini, F. Lindl, Pascale Husson, Hélène Rouault, Hassan Srour, W. Darwich, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut de Chimie de Clermont-Ferrand (ICCF), SIGMA Clermont (SIGMA Clermont)-Institut de Chimie du CNRS (INC)-Université Clermont Auvergne [2017-2020] (UCA [2017-2020])-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
chemistry.chemical_classification, Chemistry, chemistry.chemical_element, Salt (chemistry), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, imidazolium pyrrolidinium carbonate functionalized ionic liq prepn green, 0104 chemical sciences, Ion, chemistry.chemical_compound, Key point, [CHIM] Chemical Sciences, Polymer chemistry, Ionic liquid, Materials Chemistry, Salt metathesis reaction, Organic chemistry, Carbonate, [CHIM]Chemical Sciences, Lithium, 0210 nano-technology
Abstract

CAPLUS AN 2017:1472717(Journal; Online Computer File); A new, versatile, and green route to access ionic liqs. contg. carbonate groups, including 1-[2-(propyloxycarbonyloxy)ethyl]-3-Me imidazolium and N-methyl-N-[2-(propyl-oxcarbonyl) ethyl] pyrrolidinium assocd. with a bis(trifluoromethane)sulfonimide anion, [C1(C2O(CO)OC3)Im][NTf2] and [C1(C2O(CO)OC3)Py][NTf2], has been developed and characterized. The key point of this route is to avoid the metathesis reaction step with LiNTf2, which could result in ionic liqs. that are highly contaminated with LiCl salt through the coordination of lithium ions by the carbonate group. [on SciFinder(R)]

Published
2017

13. Synthesis of Amine-Containing Heterocycles by Metathesis Reactions: Recent Advances and Opportunities

Author

Philippe Compain, Damien Hazelard, Laboratoire d'innovation moléculaire et applications (LIMA), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, SYBIO, Nitrogen atom, Salt metathesis reaction, Amine gas treating, Protecting group
Abstract

Metathesis is one of the most powerful methods to access amine-containing heterocycles. However, the ability of amine to coordinate to the metal centre of almost all metathesis catalysts may limit the efficiency of this strategy. To date, the main approach to overcome these unwanted coordination events has been based on deactivation of the nitrogen atom by an electron-withdrawing protecting group. Basic amines are nevertheless not incompatible with metathesis reactions as shown by numerous recent examples described in the literature. The purpose of this review is to provide an overview of successful metathesis reactions performed with amine-containing substrates to access azacycles. The focus will be made on the different parameters that may favor the metathesis process including steric effects, amine basicity, and the nature of the catalyst.

Published
2017

14. Nickel and molybdenum containing mesoporous catalysts for ethylene oligomerization and metathesis

Author

Claudia Cammarano, Vasile Hulea, Radu Dorin Andrei, Marcel Popa, 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 'Gheorghe Asachi' Technical University of Iasi (TUIASI)

Subjects
Ethylene, Inorganic chemistry, chemistry.chemical_element, 010402 general chemistry, Metathesis, Heterogeneous catalysis, 01 natural sciences, Catalysis, oligomerization, chemistry.chemical_compound, nickel, molybdenum, Materials Chemistry, Salt metathesis reaction, ethylene, 010405 organic chemistry, Chemistry, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Nickel, heterogeneous catalysis, Molybdenum, metathesis, Mesoporous material, Nuclear chemistry
Abstract

International audience; An original Ni-AlSiO2 mesoporous catalyst (Si/Al = 6.5, 2.0 wt% Ni) was prepared using a commercialmesoporous non-ordered silica as a support. It exhibited notable catalytic behaviour for the oligomerizationof ethylene in both batch and flow mode. Thus, at 150 1C and 3.5 MPa, the catalyst washighly active (up to 130 g of oligomers per gram of the catalyst per hour), selective (C4, C6, C8, andC10 olefins, no cracking products) and stable (high conversion for 9 h on-stream). However, thecatalytic performances were slightly lower compared to those obtained with the catalyst prepared usinga mesostructured SBA-15 silica as a model support. When nickel-catalyzed oligomerization was coupledwith a metathesis reaction catalyzed by MoOx/(Al)SiO2 or MoOx/(Al)SBA-15, ethylene was efficientlyconverted into propylene. To determine the physico-chemical properties of catalysts, various techniqueswere used, such as powder X-ray diffraction, N2 sorption, 27Al MAS NMR, Raman spectroscopy and X-rayphotoelectron spectroscopy.

Published
2016

15. Facile and efficient chemical functionalization of aliphatic polyesters by cross metathesis

Author

Carine Robert, Lucie Fournier, Alice Gonzalez, Lewis Williams, Sylvie Pourchet, Joëlle Prunet, Christophe M. Thomas, PSL Research University, Chimie ParisTech, CNRS, Institut de Recherche de Chimie Paris, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), WestCHEM, University of Glasgow, CNRS, ENSCP, French Ministry of Research and Higher Education, Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), and Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
plga microspheres, phosphate-buffered solution, in-vivo degradation, Polymers and Plastics, Bioengineering, molecular-weight poly(l-lactide), 010402 general chemistry, Metathesis, 01 natural sciences, Biochemistry, [ CHIM ] Chemical Sciences, Catalysis, acid) microspheres, Copolymer, Salt metathesis reaction, enzymatic degradation, [CHIM]Chemical Sciences, Organic chemistry, Ring-opening metathesis polymerisation, cyclic anhydrides, 010405 organic chemistry, Chemistry, ring-opening copolymerization, Organic Chemistry, renewable resources, 0104 chemical sciences, Polyester, [ CHIM.POLY ] Chemical Sciences/Polymers, [CHIM.POLY]Chemical Sciences/Polymers, biodegradable polymers, Selectivity, Acyclic diene metathesis
Abstract

International audience; An effective preparation of new tailor-made macromolecular materials via a combination of two (atom-efficient) catalytic transformations is reported. First, new aliphatic polyesters with alternated composition have been prepared using a salen aluminum catalyst system. Next, the pendant vinyl moieties in those copolymers have been selectively transformed into various functional groups by metathesis in the presence of homogeneous Grubbs catalysts. The latter metathesis reaction has been optimized in terms of catalytic activity and selectivity, to define the conditions for an effective and safe procedure that does not affect the macromolecular architecture. All polymer materials have been analyzed by H-1, and C-13 NMR spectroscopy, to diagnose the catalyst selectivities in the copolymerization and metathesis processes.

Published
2016

16. Non covalent immobilization of pyrene-tagged ruthenium complexes onto graphene surfaces for recycling in olefin metathesis reactions

Author

Pierre Queval, Marc Mauduit, Caroline Bouvier, Emmanuelle Schulz, Stéphane Germain, Houssein Nasrallah, Christophe Crévisy, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Agence Nationale de la Recherche (ANR) [ANR-12-CD2I-0002 Cflow-OM], 'Region Bretagne' [SAD - GRAPH-Ru] [8734], Ministere de la Recherche et de la Technologie, Centre National de la Recherche Scientifique (CNRS), ANR-12-CDII-0002,CFLOW-OM,IMMOBILISATION DE CATALYSEURS DE METATHESE D'OLEFINES : APPLICATIONS EN PROCEDES BATCH & FLUX CONTINUS(2012), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Diene, chemistry.chemical_element, mechanism, 010402 general chemistry, Metathesis, ring-closing metathesis, 01 natural sciences, Catalysis, catalysts, ionic liquids, chemistry.chemical_compound, Ring-closing metathesis, Salt metathesis reaction, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, carbon nanotubes, 010405 organic chemistry, Ligand, n-heterocyclic carbene, pi-stacking interactions, Process Chemistry and Technology, ru carbene, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, Combinatorial chemistry, 0104 chemical sciences, Ruthenium, grubbs-hoveyda, chemistry, Pyrene, metal-complexes
Abstract

International audience; Synthesis of Hoveyda-type ruthenium complexes, modified by pyrene tags on the NHC ligand and/or the benzylidene moiety, is described. Thanks to non-covalent it-err interactions these new complexes were immobilized on carbon supports [reduced graphene oxide (rGO) or graphene] and their activity and recoverability for metatheses reactions have been studied. A SIPr-based complex possessing the pyrene function on the benzylidene ligand (C2) delivered the best results for the ring closing metathesis of diethyldiallyl malonate as benchmark reaction. The presence of additional pyrene-functionalized styrenyl-ether as ligand to the rGO-supported catalyst (C2/L@rGO) noticeably improved the recycling procedure allowing supplementary efficient catalytic runs. This may be due either to a facilitated boomerang effect or to a gradual release of the active species in solution. Finally, catalyst C2/L@rGO was proven to be successfully used to promote metathesis reactions in a multisubstrate procedure, the same supported catalyst batch being successively engaged to transform three different substrates, in diene and ene-yne RCM reactions.

Published
2016

17. Scandium and yttrium complexes of an hybrid phenoxy-amidopyridinate ligand. Use in ROP of racemic lactide

Author

Vincent Dorcet, Jad El Haj Hassan, Evgueni Kirillov, Vasily Rad'kov, Jean-François Carpentier, 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 de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
chemistry.chemical_classification, Denticity, Lactide, 010405 organic chemistry, Chemistry, Stereochemistry, Ligand, Organic Chemistry, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, Polymerization, Polymer chemistry, Materials Chemistry, Salt metathesis reaction, [CHIM]Chemical Sciences, Scandium, Physical and Theoretical Chemistry, Alkyl
Abstract

International audience; The new multidentate hybrid phenol-aminopyridine proligand _NMe2NNMe2CiPr2O_H2 (1-H2) was prepared and used in σ-bond metathesis reactions with the trialkyl precursors M(CH2SiMe3)3(THF)2 (M = Sc, Y). These reactions afforded cleanly the corresponding alkyl complexes _NMe2NNMe2CiPr2O_M(CH2SiMe3)(THF) (M = Sc (1-Sc), Y (1-Y)), which were characterized by NMR spectroscopy and microanalysis. Upon crystallization, 1-Sc disproportionates to form the bis(ligand) complex 2-Sc which was isolated and characterized by X-ray crystallography. Complexes 1-Sc and 1-Y were used as initiators in the ring-opening polymerization (ROP) of racemic lactide, alone or in combination with iPrOH, to give atactic PLAs with controlled molecular weights. © 2016 Elsevier B.V.

Published
2016

18. Ionic liquids and cyclodextrin inclusion complexes: limitation of the affinity capillary electrophoresis technique

Author

Géraldine Gouhier, Frédéric Guillen, Nadine Mofaddel, Sophie Fourmentin, David Landy, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV), Université du Littoral Côte d'Opale (ULCO), Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic chemistry, Supramolecular chemistry, Analytical chemistry, 02 engineering and technology, Ionic liquid, 010402 general chemistry, 01 natural sciences, Biochemistry, Analytical Chemistry, Ion, chemistry.chemical_compound, Capillary electrophoresis, Affinity capillary electrophoresis, Salt metathesis reaction, Cyclodextrin, [CHIM]Chemical Sciences, chemistry.chemical_classification, Chemistry, technology, industry, and agriculture, Isothermal titration calorimetry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Binding constants, 0210 nano-technology, Stoichiometry
Abstract

International audience; The state of the art of inclusion complex formation between cyclodextrins and ionic liquids is reported. Mechanisms, stoichiometries, and binding constants are summarized and classified by anion. We investigated the supramolecular interactions between the β-cyclodextrin cavity and six ionic liquids based on 1-dodecyl-3-methylimidazolium by affinity capillary electrophoresis and compared the results with those obtained by isothermal titration calorimetry. We show that the presence of basic or acidic buffers leads to a metathesis reaction, underlining the limitation of the affinity capillary electrophoresis technique.

Published
2016

19. Production of Sodium Dihydrogen Phosphate Using Sodium Chloride and Orthophosphoric Acid

Author

Pham Minh Doan, Sharrock Patrick, Nzihou Ange, Centre de recherche d'Albi en génie des procédés des solides divisés, de l'énergie et de l'environnement (RAPSODEE), Centre National de la Recherche Scientifique (CNRS)-IMT École nationale supérieure des Mines d'Albi-Carmaux (IMT Mines Albi), and Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)

Subjects
PHOSPHATE MONOSODIQUE, General Chemical Engineering, Sodium, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Sodium phosphates, Chemical synthesis, Pyrophosphate, Industrial and Manufacturing Engineering, 0104 chemical sciences, chemistry.chemical_compound, [SPI]Engineering Sciences [physics], chemistry, Sodium hydroxide, Salt metathesis reaction, 0210 nano-technology, Hydrogen chloride, Sodium carbonate
Abstract

International audience; Up-to-date, standard synthesis processes of sodium phosphates are based on the neutralization of orthophosphoric acid by sodium hydroxide or sodium carbonate. To the best of our knowledge, the reaction between sodium chloride and orthophosphoric acid has not yet been reported in the literature. This study demonstrated the feasibility of the synthesis of sodium dihydrogen phosphate by the reaction of sodium chloride with orthophosphoric acid. A detailed parametric study was done, wherein the influence of reaction temperature, air flow rate, water addition flow rate, and reaction time was investigated. As expected, the evacuation of hydrogen chloride (HCl) was crucial for getting high conversion of NaCl to HCl. The highest conversion of NaCl to HCl reached 91% after 24 h of synthesis reaction. Sodium dihydrogen phosphate (NaH2PO4) was the main product. Pyrophosphate (P2O74-) was only formed at trace amounts, and any trace of trimetaphosphate (P3O93-) was observed.

Published
2015

20. Metallacyclobutanes from Schrock-Type d0 Metal Alkylidene Catalysts: Structural Preferences and Consequences in Alkene Metathesis

Author

Christophe Copéret, Xavier Solans-Monfort, Odile Eisenstein, departament de Quimica, Universitat Autònoma de Barcelona (UAB), Department of Chemistry and Applied Biosciences [ETH Zürich] (D-CHAB), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), 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
chemistry.chemical_classification, Alkene, Aryl, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Metathesis, Medicinal chemistry, Catalysis, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Trigonal bipyramidal molecular geometry, chemistry.chemical_compound, chemistry, Alkoxy group, Salt metathesis reaction, Organic chemistry, Physical and Theoretical Chemistry, Alkyl
Abstract

International audience; Metallacyclobutanes have been observed as intermediates in the alkene metathesis reaction, with the 5-coordinated metal center, in a trigonal bipyramidal or a square-planar coordination. Previous calculations have shown that only the trigonal bipyramidal form is directly on the reaction pathway of alkene metathesis. The square-pyramidal form, which is obtained by a trigonal-bipyramidal (TBP)-square-based pyramidal (SP) interconversion at the metal, is an intermediate that can be responsible for catalyst deactivation. This computational study aimed at establishing the factors that control the properties of the two metallacyclobutanes (structural and 13C NMR features, stability, and TBP-SP interconversion) that can influence the efficiency of the metathesis reaction. Metallacyclobutanes resulting from the addition of ethene to a large set of methylidene complexes where the metal fragment is M(E)(X)(Y) (M = Mo or W; E = alkyl imido, aryl imido, or oxo), (X and Y) = alkyl, pyrrolyl, alkoxy and fluoroalkoxy, and large monoaryloxy) have been studied by density functional calculations (B3PW91, and M06). From the study of these numerous complexes that include in particular all characterized complexes, properties of the metallacyclobutanes could be derived: Metallacyclobutanes with W are more stable than those with Mo relative to reactants; electron withdrawing ligands stabilize the two isomeric forms of the metallacyclobutane but more the TBP than the SP form, and conversely, electron donating ligands destabilize both forms but more the TBP isomer. The energy barrier for the TBP-SP interconversion is found to be lower than that for the productive ethene metathesis pathway for W complexes but is generally higher for Mo species. These facts rationalize the experimental evidence and accounts in particular for the high efficiency of the Mo catalysts.

Published
2015

21. Ytterbium(III) Complexes Coordinated by Dianionic 1,4-Diazabutadiene Ligands

Author

Georgy K. Fukin, Joulia Larionova, Wolfgang Scherer, Boris G. Shestakov, Alexander A. Trifonov, Jérôme Long, Tatiana V. Magdesieva, Tatyana V. Mahrova, Konstantin A. Lyssenko, Anton V. Cherkasov, Christoph Hauf, Oleg A. Levitskiy, Russian Acad Sci, GA Razunaev Inst Organomet Chem, Russian Academy of Sciences [Moscow] (RAS), G. A. Razuvaev Institute of Organometallic Chemistry, 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), A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Institute of Physics, University of Augsburg, Universität Augsburg [Augsburg], and Lomonosov Moscow State University (MSU)

Subjects
Ytterbium, Cyclopentadienyl anion, 010405 organic chemistry, Stereochemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Molar ratio, Salt metathesis reaction, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

A series of new Yb(III) complexes XYb(DAD)2–(L) (X = C5Me5, C5Me4H, N(SiMe3)2, tBuO; DAD = 2,6-R″2C6H3N═C(R′)-C(R′)═NC6H3R″2-2,6, R′ = H, Me, R″ = Me, iPr; L = thf, dme) coordinated by redox-active diazabutadiene ligands in dianionic form were synthesized and characterized. The half-sandwich complexes Cp#Yb(DAD)2–(THF) (Cp# = C5Me5, C5Me4H) were synthesized by the reactions of the ytterbocenes Cp#2Yb(THF)2 with the corresponding DADs in a 1:1 molar ratio. These reactions are accompanied by oxidation of the Yb(II) to Yb(III), cleavage of one Cp#–Yb bond, oxidation of cyclopentadienyl anion, and reduction of the diazabutadiene to dianionic form. It was found that the substituents by the DAD nitrogens (2,6-iPr2C6H3 vs 2,6-Me2C6H3) and imino carbons (H vs Me) do not affect the reaction outcome and afford Cp#Yb(DAD)2–(thf). The amido and alkoxo derivatives XYb(DAD)2–(dme) (X = N(SiMe3)2, tBuO) were obtained by the salt metathesis reactions of the in situ generated species [XYbCl2(thf)n] and Na2(thf)n[2,6-iPr2C...

Published
2015

22. Direct Immobilization of Ru-Based Catalysts on Silica: Hydrogen Bonds as Non-Covalent Interactions for Recycling in Metathesis Reactions

Author

Emmanuelle Schulz, Marc Mauduit, Caroline Magnier, Houssein Nasrallah, Diana Dragoe, Christophe Crévisy, Laboratoire de physique de l'état condensé (LPEC), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), IFP Energies nouvelles (IFPEN), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique, ANR-12-CD2I-0002 Cflow-OM, Agence Nationale de la Recherche (ANR), Ministère de la Recherche, ANR-12-CDII-0002,CFLOW-OM,IMMOBILISATION DE CATALYSEURS DE METATHESE D'OLEFINES : APPLICATIONS EN PROCEDES BATCH & FLUX CONTINUS(2012), Centre National de la Recherche Scientifique (CNRS)-Le Mans Université (UM), 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), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, XPS analysis, Hydrogen bond, Organic Chemistry, chemistry.chemical_element, Metathesis, Catalysis, Ruthenium, Inorganic Chemistry, chemistry, catalyst reuse, silica, Salt metathesis reaction, Moiety, Ring-opening metathesis polymerisation, Non-covalent interactions, Organic chemistry, [CHIM]Chemical Sciences, metathesis, Physical and Theoretical Chemistry, ruthenium
Abstract

International audience; The commercially available M71-SIPr ruthenium precatalyst was deposited on silica, with the aim to develop a simple procedure for catalyst recovery in metathesis reactions. Various spectroscopic analyses revealed that the impregnation resulted from hydrogen bonding interactions, specifically with the carbonyl group of the trifluoroacetamide moiety of the complex. These interactions were, furthermore, responsible for catalytic improvement through a facilitated release of the active ruthenium species. The silica-supported complex proved to be an efficient catalyst for the promotion of various olefin metathesis reactions in a multisubstrate procedure. The catalytic material was easily recovered by simple filtration and delivered the targeted products in high yield for seven consecutive runs

Published
2015

23. Access to Fluorinated Lactams through Ring-Closing Metathesis of Reluctant Fluoroalkenes Promoted by Appropriate Substitution of a Double Bond

Author

Annie-Claude Gaumont, Marc Mauduit, Xavier Pannecoucke, David Guerin, Isabelle Dez, Samuel Couve-Bonnaire, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU), 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), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Le Havre Normandie (ULH), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
chemistry.chemical_classification, Double bond, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Combinatorial chemistry, Catalysis, Ruthenium, fluoroalkene, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Ring-closing metathesis, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Salt metathesis reaction, Organic chemistry, Ring-opening metathesis polymerisation, Reactivity (chemistry), N-heterocyclic carbenes, ruthenium, [CHIM.CHEM]Chemical Sciences/Cheminformatics, Acyclic diene metathesis, olefin metathesis
Abstract

International audience; Challenging homogeneous ring-closing metathesis reaction has been developed with reluctant fluorinated substrates. The combination of various parameters, such as the use of fluorinated aromatic solvent and appropriate substitution of the double bonds, allowed us to reach high levels of reactivity, leading to high yields of both new relevant five- and six-membered lactams containing a fluorinated double bond. The electron density of the substituted double bond seems to play a crucial role in the reaction. The formation of six-membered rings proved to be highly efficient, even at low catalyst loading and low temperature.

Published
2014

24. Olefin Metathesis in Green Organic Solvents and without Solvent

Author

Cédric Fischmeister, Christian Bruneau, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Karol Grela, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Green chemistry, Materials science, glycerol, 010402 general chemistry, Metathesis, 01 natural sciences, Catalysis, chemistry.chemical_compound, Ring-closing metathesis, supercritical carbon dioxide, Salt metathesis reaction, Organic chemistry, olefin metathesis, organic carbonate, [CHIM]Chemical Sciences, Supercritical carbon dioxide, poly(ethylene glycol), 010405 organic chemistry, poly(ethylene glycol) (PEG), 0104 chemical sciences, Solvent, chemistry, 13. Climate action, methyl decanoate, green organic solvent, Dimethyl carbonate
Abstract

International audience; This chapter focuses on olefin metathesis transformations in green(er) organic solvents, including supercritical carbon dioxide (scCO2) and organic carbonates, in particular dimethyl carbonate (DMC) and poly(ethylene glycol) (PEG). It reviews the domain of a solvent very often quoted as the greenest or best solvent in green chemistry textbooks, namely, no solvent or solventless conditions. DCM is often used in ruthenium-catalyzed metathesis reactions as it is in general a good catalyst solvent. Recently, ring closing metathesis (RCM) of diethyl diallylmalonate (DEDAM) and cross metathesis of allylbenzene with cis-1,4-diacetoxy-2-butene were studied, both under solvent-free conditions and in methyl decanoate, a renewable and environmentally benign solvent derived from fatty acid derivatives. More recently, the synthesis of nitrogen containing heterocycles by ruthenium catalyzed RCM using low catalyst loading was studied by Grubbs.

Published
2014

25. The role of 5f-orbital participation in unexpected inversion of the σ-bond metathesis reactivity trend of triamidoamine thorium( iv ) and uranium( iv ) alkyls

Author

Christos E. Kefalidis, Laurent Maron, Jian Fang, Stephen T. Liddle, Alexander J. Blake, William Lewis, Benedict M. Gardner, Peter A. Cleaves, School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK. Code (UMR, EA, ...), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Lanzhou University, Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)

Subjects
[PHYS]Physics [physics], 010405 organic chemistry, Thermal decomposition, Inorganic chemistry, Thorium, chemistry.chemical_element, Ionic bonding, General Chemistry, Uranium, 010402 general chemistry, Metathesis, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Salt metathesis reaction, Bibenzyl, [CHIM]Chemical Sciences, Reactivity (chemistry)
Abstract

International audience; We report on the role of 5f-orbital participation in the unexpected inversion of the s-bond metathesis reactivity trend of triamidoamine thorium(IV) and uranium(IV) alkyls. Reaction of KCH 2 Ph with [U(Tren TIPS)(I)] [2a, Tren TIPS ¼ N(CH 2 CH 2 NSiPr i 3) 3 3À ] gave the cyclometallate [U {N(CH 2 CH 2 NSiPr i 3) 2 (CH 2 CH 2 NSiPr i 2 C[H]MeCH 2)}] (3a) with the intermediate benzyl complex not observable. In contrast, when [Th(Tren TIPS)(I)] (2b) was treated with KCH 2 Ph, [Th(Tren TIPS)(CH 2 Ph)] (4) was isolated; which is notable as Tren N-silylalkyl metal alkyls tend to spontaneously cyclometallate. Thermolysis of 4 results in the extrusion of toluene and formation of the cyclometallate [Th {N(CH 2 CH 2 NSiPr i 3) 2 (CH 2 CH 2 NSiPr i 2 C[H]MeCH 2)}] (3b). This reactivity is the reverse of what would be predicted. Since the bonding of thorium is mainly electrostatic it would be predicted to undergo facile cyclometallation, whereas the more covalent uranium system might be expected to form an isolable benzyl intermediate. The thermolysis of 4 follows well-defined first order kinetics with an activation energy of 22.3 AE 0.1 kcal mol À1 , and Eyring analyses yields DH ‡ ¼ 21.7 AE 3.6 kcal mol À1 and DS ‡ ¼ À10.5 AE 3.1 cal K À1 mol À1 , which is consistent with a s-bond metathesis reaction. Computational examination of the reaction profile shows that the inversion of the reactivity trend can be attributed to the greater f-orbital participation of the bonding for uranium facilitating the s-bond metathesis transition state whereas for thorium the transition state is more ionic resulting in an isolable benzyl complex. The activation barriers are computed to be 19.0 and 22.2 kcal mol À1 for the uranium and thorium cases, respectively, and the latter agrees excellently with the experimental value. Reductive decomposition of "[U(Tren TIPS)(CH 2 Ph)]" to [U(Tren TIPS)] and bibenzyl followed by cyclometallation to give 3a with elimination of dihydrogen was found to be endergonic by 4 kcal mol À1 which rules out a redox-based cyclometallation route for uranium.

Published
2014

26. Interest of the Precatalyst Design for Olefin Metathesis Operating in a Discontinuous Nanofiltration Membrane Reactor

Author

Cédric Fischmeister, Saurabh Shahane, Ghassan Nasser, Thierry Renouard, Murielle Rabiller-Baudry, Christian Bruneau, 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), French National Research Agency. Grant Number: ANR-09-CP2D-11-01, 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), and ANR-09-CP2D-0001,AEPRC2V,Une Approche Economique de l'intégration des dimensions socio-économiques et techniques dans les Programmes de Recherche en Chimie Doublement Verte - An Economical Approach of Integration of socio-economical, and technological dimensions into Research'(2009)

Subjects
chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, organic solvent nanofiltration, 01 natural sciences, Catalysis, chemistry.chemical_compound, [CHIM.GENI]Chemical Sciences/Chemical engineering, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Salt metathesis reaction, Organic chemistry, olefin metathesis, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, ruthenium, ComputingMilieux_MISCELLANEOUS, Membrane reactor, 010405 organic chemistry, Chemistry, [SDE.IE]Environmental Sciences/Environmental Engineering, General Chemistry, Toluene, homogeneous catalysis, 0104 chemical sciences, Ruthenium, Membrane, Chemical engineering, membrane reactors, Nanofiltration
Abstract

This study aimed at evaluating the impact of the structure of several new olefin metathesis homogeneous catalysts on the performances of a membrane reactor running in a discontinuous mode and equipped with a nanofiltration membrane that was stable in toluene. A set of tailor-made ruthenium-based precatalysts were prepared with a first objective of enhancing the retention of the precatalyst, that is the stable source of the active catalyst, by organic solvent nanofiltration using a commercial polyimide membrane (Starmem 122). These prototype precatalysts were designed taking into account both the molecular weight and the physicochemical characteristics allowing up to 99.6 % retention of the precatalyst in toluene. The new precatalysts were then engaged in a model ring-closing metathesis reaction in the membrane reactor. Results, expressed as the precatalyst apparent turnover number, showed significant differences according to the selected precatalyst, underlining that the membrane reactor advantages and limitations were closely linked to the intrinsic activity of the catalyst. In addition to the retention of the precatalyst by the membrane, a major parameter was the percentage of the precatalyst really activated during the first load of the substrate since that controls the residual amount of precatalyst to be engaged in the following reaction cycle. The main consequence was the proposal of different running modes consisting of a cascade of synthesis in batch mode and separation by the membrane or a membrane reactor process.

Published
2013

27. Catalytic applications of recyclable silica immobilized NHC-ruthenium complexes

Author

Roser Pleixats, Xavier Cattoën, Michel Wong Chi Man, Amàlia Monge-Marcet, 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), Chemistry department, Universitat Autònoma de Barcelona (UAB), and thèse co-tutelle UAB-ENSCM

Subjects
Hydrosilylation, Olefin metathesis, NHC ruthenium alkylidene, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Supported catalysis, Drug Discovery, Polymer chemistry, Salt metathesis reaction, Organic chemistry, Organosilica, 010405 organic chemistry, Ligand, Organic Chemistry, Alkyne hydrosilylation, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Toluene, 0104 chemical sciences, Ruthenium, chemistry, Selectivity
Abstract

8 pages; International audience; A monosilylated HoveydaeGrubbs ruthenium alkylidene has been prepared and grafted through the NHC ligand to a mesostructured silica, in refluxing toluene or at room temperature, giving two new organiceinorganic hybrid silica materials M2 and M3, respectively. While M3 exhibited good performances in several metathesis reactions, M2 showed good selectivity in the hydrosilylation of terminal alkynes, where the b-(Z)-vinylsilane was obtained as major product. Recycling of the supported catalysts without significant decrease in activity and selectivity was proven for at least three cycles in both transformations.

Published
2013

28. Screening of a selection of commercially available homogeneous Ru-catalysts in valuable olefin metathesis transformations

Author

Olivier Baslé, Aurélien Bellec, Christophe Crévisy, Frédéric Caijo, Marc Mauduit, Fabien Tripoteau, Oliver Briel, 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), CNRS, Ministère de la Recherche et de la Technologie, Bretagne-Valorisation, Rennes Métropole, European Project, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
RING-CLOSING METATHESIS, Olefin metathesis, BEARING, 010405 organic chemistry, Chemistry, LACTONES, NHC LIGAND, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, HETEROCYCLIC CARBENE LIGANDS, Catalysis, 0104 chemical sciences, Exaltolide, CATHEPSIN K-INHIBITOR, LARGE-SCALE SYNTHESIS, Homogeneous, Salt metathesis reaction, Organic chemistry, NOBEL LECTURE, COMPLEXES, CYCLOADDITION-ALLYLIC REARRANGEMENT
Abstract

International audience; A library of thirteen different commercially available Ru-based catalysts was evaluated in valuable metathesis reactions for the production of fragrance and bioactive molecule precursors. Rigorous library screening clearly illustrated the different catalytic behaviour of the catalyst selection and highlighted its significant advantage to provide efficiency in specific metathesis applications. Interestingly, this strategy offered substantial improvement over the state of the art, with the efficient synthesis of the macrocyclic Exaltolide 2 at low catalyst loading and dilution conditions.

Published
2013

29. Alkylyttrium Complexes of Amidine-Amidopyridinate Ligands. Intramolecular C(sp3)-H Activation and Reactivity Studies

Author

Alexander A. Trifonov, Evgeny Kirillov, Vasily Rad'kov, Jean-François Carpentier, Vincent Dorcet, 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 de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Denticity, 010405 organic chemistry, Organic Chemistry, Nuclear magnetic resonance spectroscopy, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Toluene, 0104 chemical sciences, Inorganic Chemistry, Amidine, chemistry.chemical_compound, Crystallography, chemistry, Intramolecular force, Salt metathesis reaction, Reactivity (chemistry), Physical and Theoretical Chemistry, Brønsted–Lowry acid–base theory
Abstract

International audience; The new multidentate amidine-aminopyridine proligand {NMe2NNMe2CMeNMe2}H (1) was used in σ-bond metathesis reactions with the trialkyl precursors Y(CH2SiMe3)3(THF)2 and Y(CH2C6H4-o-NMe2)3. These reactions generate the dialkyl complexes {NMe2NNMe2CMeNMe2}Y(CH2SiMe3)2(THF) (2a) and {NMe2NNMe2CMeNMe2}Y(CH2C6H4-o-NMe2)2 (2b), respectively, which were characterized by NMR spectroscopy and microanalysis (for 2b). Complex 2a is unstable at −30 °C in toluene and selectively undergoes intramolecular C(sp3)-H activation to give {NMe2NNMe2CMeNMe-CH2}Y(CH2SiMe3)(THF) (2a′), authenticated by X-ray crystallography, NMR spectroscopy, and elemental analysis. The reactivity of 2a′ toward a number of Lewis and Brønsted acids and bases as well as oxidants and reductants was explored. In the course of these studies, the new complexes {NMe2NNMe2CMeNMeCH2B(C6F5)3}Y(CH2SiMe3)(THF) (3), [{NMe2NNMe2CMeNMeCH2}Y(CH2SiMe3)(THF)x]+[BPh4]− (4), {NMe2NNMe2CMeNMeCH2}Y(iPrNC(PPh2)NiPr) (5), [{NMe2NNMe2CMeNMe2}Y{(μ2-BH3)(μ2-NH)}]2 (6), and [{NMe2NNMe2CMeNMeCH2(μ-O)}Y(CH2SiMe3)]2 (7) were isolated and characterized by NMR spectroscopy and X-ray crystallography and microanalysis (for 6 and 7). Complex 6 was found to be active in the ROP of rac-lactide, affording slightly heterotactic-enriched PLAs.

Published
2013

30. Synthesis of Nitrogen-Containing Heterocycles via Ring-Closing Ene-Ene and Ene-Yne Metathesis Reactions: An Easy Access to 1-and 2-Benzazepine Scaffolds and Five- and Six-Membered Lactams

Author

Max Malacria, Francesco Tibiletti, Erica Benedetti, Michela Lomazzi, Louis Fensterbank, Giovanni Palmisano, Jean-Philippe Goddard, Andrea Penoni, Chimie-Biologie-Innovation (UMR 8231) (CBI), 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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Ministero dell'Istruzione, dell'Universita e della Ricerca (PRIN), and Programmi di Ricerca Scientifica di Rilevante Interesse Nazionale [prot. 2008M3Y5WX]

Subjects
010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Regioselectivity, regioselective reactions, 010402 general chemistry, Ring (chemistry), Metathesis, 01 natural sciences, Benzazocine, Combinatorial chemistry, benzazepine scaffolds, Catalysis, 0104 chemical sciences, Benzazepine, chemistry.chemical_compound, Grubbs catalysts, ring closing ene-yne metathesis, chemistry, Salt metathesis reaction, Moiety, ring closing ene-ene metathesis, nitrogen heterocycles, lactams, Ene reaction
Abstract

International audience; Novel regioselective ring closing ene-yne metathesis provided an efficient access to different substituted 1-benzazepine scaffolds. The reported synthetic approach could also be used as a powerful tool for the selective formation of a highly functionalizable 2-benzazepine core. This synthetic protocol was even proved to be an efficient way to obtain a functionalizable benzazocine derivative. By modifying the structure of the starting materials, the optimized cyclization finally proved to be a suitable technique to obtain five-and six-membered lactams, enhancing the synthetic application of our method. Five-and six-membered lactams were efficiently prepared by ring-closing metathesis involving the loss of ethylene moiety and affording highly functionalizable compounds showing both electron-withdrawing substituents and electron-donor groups.

Published
2012

31. Comprehensive study on olefin metathesis in PEG as an alternative solvent under microwave irradiation

Author

Jean Martinez, Xavier Bantreil, Frédéric Lamaty, Laura Aringhieri, Evelina Colacino, Mohammed Sidi-Ykhlef, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Isomerization, Polyethylene glycol, Metathesis, macromolecular substances, 010402 general chemistry, 01 natural sciences, Catalysis, Ruthenium, Microwave-assisted synthesis, chemistry.chemical_compound, Salt metathesis reaction, Organic chemistry, Ring-opening metathesis polymerisation, Physical and Theoretical Chemistry, Hydride, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, technology, industry, and agriculture, 0104 chemical sciences, Solvent, chemistry, Acyclic diene metathesis
Abstract

International audience; Polyethylene glycols (PEGs) are non-toxic, biodegradable and sustainable organic solvents, which find a large application in the chemical and pharmaceutical industry. In this study, we present the ring-closing metathesis reaction (RCM) in PEG under microwave irradiation. Several benchmark substrates, yielding 5- to 6-membered rings featuring di- or tri-substituted olefins, were evaluated. This study demonstrated that PEGs are suitable solvent for olefin metathesis. However, depending on the substrate/catalyst couple, isomerization may occur.

Published
2012

32. Regioselective Metathesis Reactions of Various Poly-unsaturated Ketones and Alcohols

Author

Nicolas Galy, Maurice Santelli, Henri Doucet, Chahinez Aouf, Laboratoire Chimie Provence (LCP), Université de Provence - Aix-Marseille 1-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CNRS, the Ministère de l'Education Nationale, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
chemistry.chemical_classification, Propenyl, Ketone, cyclization, 010405 organic chemistry, Regioselectivity, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, 0104 chemical sciences, lactones, Inorganic Chemistry, Ring-closing metathesis, chemistry, indenols, Salt metathesis reaction, Ring-opening metathesis polymerisation, Organic chemistry, metathesis, Acyclic diene metathesis
Abstract

International audience; The reactivity for metathesis reaction of some polyunsaturated cyclopentanols, and of a polyunsaturated ketone bearing vinyl groups or vinyl and propenyl groups has been examined. In the presence of two of these reactants, depending on the ruthenium catalyst employed, either the ring closing metathesis or the cross-coupling metathesis was observed.

Published
2010

33. Immobilisation of an ionically tagged Hoveyda catalyst on a supported ionic liquid membrane: An innovative approach for metathesis reactions in a catalytic membrane reactor

Author

Adel Keraani, Christian Bruneau, Murielle Rabiller-Baudry, Cédric Fischmeister, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Membrane reactor, 010405 organic chemistry, Catalyst support, Metathesis, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Ionic liquid, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Catalytic membrane reactor, Catalysis, Nanofiltration, 0104 chemical sciences, chemistry.chemical_compound, Membrane, chemistry, Chemical engineering, Salt metathesis reaction, Organic chemistry, Immobilisation
Abstract

International audience; This study aimed at developing an innovative strategy to recycle homogeneous olefin metathesis catalysts by the combination of complementary green processes, namely organic solvent nanofiltration coupled with ionic liquid advantages. The immobilisation of an ionically tagged Hoveyda catalyst in an ionic liquid previously supported on a solvent-resistant polyimide membrane (Starmem 228) was prepared leading to an original catalytic membrane successfully used in a membrane reactor for a model metathesis reaction.

Published
2010

34. Gold- and silver-based ionic liquids: modulation of luminescence depending on the physical state

Author

Yannick Guari, José M. López-de-Luzuriaga, Christophe Blanc, Philippe Dieudonné, Christian Guérin, Joulia Larionova, Miguel Monge, Alexei Tokarev, 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), Universidad de La Rioja (UR), Laboratoire Charles Coulomb (L2C), Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des colloïdes, verres et nanomatériaux (LCVN), and Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Photoluminescence, 010405 organic chemistry, Intermolecular force, State (functional analysis), 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Modulation, Ionic liquid, Salt metathesis reaction, Physical chemistry, Organic chemistry, Phosphorescence, Luminescence, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract

International audience; A series of gold- and silver-containing ionic liquids, [CnMIM][M(CN)2] (M = Au, Ag; n = 12, 14, 18), prepared by metathesis reactions, present luminescence depending on their physical state i.e. crystalline or smectic A phases. The photoluminescent measurements as well as DFT calculations suggest that the modulation of aurophilic intermolecular interactions are responsible for this phosphorescent behaviour.

Published
2010

35. Imidazolium-oxazoline salts in ruthenium catalysed allylic substitution and cross metathesis of formed branched isomers

Author

Hamed Ben Ammar, Christian Bruneau, Béchir Ben Hassine, Cédric Fischmeister, Pierre H. Dixneuf, laboratoire de chimie organique appliquée, Faculté des sciences de Gabes, Laboratoire de Synthèse Organique Asymétrique et Catalyse Homogène, Faculté des Sciences de Monastir (FSM), Université de Monastir - University of Monastir (UM)-Université de Monastir - University of Monastir (UM), 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 de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Substitution reaction, Allylic rearrangement, 010405 organic chemistry, Nitrogen heterocycles, Regioselectivity, chemistry.chemical_element, Homogeneous catalysis, Oxazoline, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Medicinal chemistry, Allylic substitution, 0104 chemical sciences, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Salt metathesis reaction, Organic chemistry, Carbene ligands
Abstract

International audience; Imidazolium-oxazoline chlorides have been prepared from chloroacetonitrile and used to generate bidentate mixed NHC-oxazoline ligands for ruthenium-catalyzed substitution of cinnamyl chloride by phenols. These ligands associated to [RuCp*(MeCN)3][PF6] promote allylic substitution reactions at room temperature with high regioselectivity in favour of the branched isomers giving terminal alkenes. These allylic ethers have been involved in further ruthenium-catalyzed cross metathesis reactions with electron-deficient olefins to give unsaturated esters and aldehydes.

Published
2010

36. Zinc(II) Complexes Based on Sterically Hindered Hydrotris(pyrazolyl)borate Ligands: Synthesis, Reactivity and Solid-State Structures

Author

Jean-François Carpentier, Joice S. Klitzke, Osvaldo L. Casagrande, Thierry Roisnel, Instituto de Quimica - Universidade Federal do Rio Grande do Sul, Universidade Federal do Rio Grande do Sul [Porto Alegre] (UFRGS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Steric effects, chemistry.chemical_classification, Denticity, 010405 organic chemistry, Chemistry, Ligand, Dimer, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, Salt metathesis reaction, Organic chemistry, Reactivity (chemistry), Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

The coordination chemistry and reactivity of zinc(II) complexes supported by monoanionic hydrotris(pyrazolyl)borate ligands substituted by 3,3,3-mesityl groups (Tp Ms ) and 3,3,5-mesityl groups (Tp Ms∗ ) have been investigated. Salt metathesis of ZnCl 2 , ZnEt 2 , and Zn(OAc) 2 with Tl[Tp Ms ] or Tl[Tp Ms∗ ] cleanly afforded the corresponding compounds Tp Ms ZnCl ( 1 ), Tp Ms ZnEt ( 2 ), Tp Ms∗ ZnEt ( 3 ), and Tp Ms ZnOAc ( 5 ). Compound 3 slowly disproportionates in benzene solution to afford the bis(ligand) complex (κ 2 -Tp Ms∗ ) 2 Zn ( 4 ). Acetate complex 5 as well as Tp Ms ZnOCOPh ( 6 ) and [Tp Ms∗ ZnOAc] 2 ( 7 ) were alternatively prepared by acidolysis of the parent ethyl complexes ( 2 , 3 ) with the corresponding carboxylic acid. No reaction was observed between 2 and 3 and alcohols (ROH; R = Et, i Pr, Bn), while salt metathesis reactions of ZnEt(OR) with Tl[Tp Ms ] led to 2 instead of the desired zinc-alkoxide complex. Compounds 1 – 7 were characterized by elemental analysis, 1 H and 13 C NMR spectroscopy, as well as by X-ray diffraction studies for 1 , 2 , 4 , 5 and 7 . The former compounds adopt a monomeric structure in the solid state while [Tp Ms∗ ZnOAc] 2 ( 7 ) exists as an anti - syn bridged acetate dimer. Complex 4 is four-coordinated, featuring a rare bidentate coordination mode of the Tp Ms∗ ligands. The results are rationalized in terms of the variable steric constraint around the zinc atom provided by the Tp Ms and Tp Ms∗ ligands.

Published
2009

37. Olefin metathesis in ionic liquids

Author

Karol Grela, Paweł Śledź, Marc Mauduit, 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 de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Olefin fiber, Materials science, Olefin metathesis, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, Catalysis, chemistry.chemical_compound, chemistry, Ionic liquid, Salt metathesis reaction, Organic chemistry, Ring-opening metathesis polymerisation, ComputingMilieux_MISCELLANEOUS
Abstract

This tutorial review covers the use of ionic liquids as (co)solvents for the olefin metathesis reaction. Olefin metathesis is a simple and effective synthetic tool used to create many compounds which otherwise would require complex multistep syntheses. It is expected that the application of ionic liquids (IL) as well as the development of IL-enabled catalysts and separation techniques will create a green aspect to this important methodology.

Published
2008

38. Ring-Closing Metathesis in the Synthesis of BC Ring-Systems of Taxol

Author

Cong Ma, Stéphanie Schiltz, Joëlle Prunet, Xavier F. Le Goff, Laboratoire de synthèse organique (DCSO), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire Hétéroéléments et Coordination (DCPH)

Subjects
Models, Molecular, Magnetic Resonance Spectroscopy, Paclitaxel, Stereochemistry, Taxol, chemistry.chemical_element, 010402 general chemistry, Metathesis, Ring (chemistry), 01 natural sciences, Catalysis, Mass Spectrometry, Ring-Closing Metathesis, Ring-closing metathesis, Salt metathesis reaction, Moiety, Protecting group, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, Antineoplastic Agents, Phytogenic, 0104 chemical sciences, Ruthenium, Cyclization
Abstract

International audience; BC ring-systems of taxol with different or no protecting group for the C1,C2 diol moiety have been efficiently synthesized. The 8-membered B ring is formed by a ring-closing metathesis (RCM) between the C10 and C11 carbons. The influence of the 1,2-diol protecting group on the RCM reaction has been studied in details.

Published
2008

39. Reluctant Cross-Metathesis Reactions: The Highly Beneficial Effect of Microwave Irradiation

Author

Thomas Boddaert, Yoann Coquerel, Jean Rodriguez, Antoine Michaut, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Microwave irradiation, Salt metathesis reaction, 010402 general chemistry, Metathesis, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences
Abstract

carbene complexes ; catalysis ; cross coupling ; metathesis ; olefination; International audience; The beneficial effect of microwave irradiation versus classical thermal conditions is demonstrated through a series of comparative cross-metathesis reactions.

Published
2007

40. Synthesis of allocolchicines using sequential ring-closing enyne metathesis - Diels - Alder reactions

Author

Issam Hanna, François-Didier Boyer, Chimie Biologique (UCB), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, Laboratoire de synthèse organique (DCSO), Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Magnetic Resonance Spectroscopy, Enyne, 010405 organic chemistry, Chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Medicine, 010402 general chemistry, Metathesis, Enyne metathesis, Ring (chemistry), 01 natural sciences, Biochemistry, 0104 chemical sciences, Colchicum, Salt metathesis reaction, Diels alder, Indicators and Reagents, Physical and Theoretical Chemistry, Colchicine
Abstract

International audience; New allocolchinoids having functionality in the C ring at position C10 or C11 have been synthesized using the enyne ring-closing metathesis (RCM) reaction for construction of the seven-membered ring and a Diels-Alder-aromatization sequence for the elaboration of the aromatic ring C. © 2007 American Chemical Society.

Published
2007

41. Synthesis of the tricyclic core of colchicine via a dienyne tandem ring-closing metathesis reaction

Author

François-Didier Boyer, Issam Hanna, Chimie Biologique (UCB), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, Laboratoire de synthèse organique (DCSO), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
chemistry.chemical_classification, Tandem, Molecular Structure, 010405 organic chemistry, Stereochemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Total synthesis, One-Step, Stereoisomerism, 010402 general chemistry, Metathesis, 01 natural sciences, Biochemistry, 0104 chemical sciences, Ring-closing metathesis, Cyclization, Alkynes, Salt metathesis reaction, Physical and Theoretical Chemistry, Colchicine, Acyclic diene metathesis, Tricyclic
Abstract

International audience; The synthesis of the tricyclic framework of colchicine has been achieved using a tandem ring-closing metathesis reaction of dienynes as the key step. In this process, both seven-membered rings B and C were formed in one step. Oxidation of tertiary allylic alcohol derived from the tandem metathesis product furnished an intermediate in the total synthesis of colchicine. © 2007 American Chemical Society.

Published
2007

42. Sustainable Concepts in Olefin Metathesis

Author

Andreas Kirschning, Karol Grela, Hervé Clavier, Steven P. Nolan, Marc Mauduit, 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), Institute of Organic Chemistry [Warsaw], Polska Akademia Nauk = Polish Academy of Sciences (PAN), Institute of Chemical Research of Catalonia (ICIQ), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and 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)

Subjects
Green chemistry, Olefin metathesis, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, Context (language use), General Chemistry, General Medicine, Alkenes, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, Catalysis, Ruthenium, 0104 chemical sciences, Homogeneous, Salt metathesis reaction, Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerization reactions, only a limited number of industrial processes use olefin metathesis. This is mainly due to difficulties associated with removing ruthenium from the final products. In this context, a number of studies have been carried out to develop procedures for the removal of the catalyst or the products of catalyst decomposition, however, none are universally attractive so far. This situation has resulted in tremendous activity in the area dealing with supported or tagged versions of homogeneous catalysts. This Review summarizes the numerous studies focused on developing cleaner ruthenium-catalyzed metathesis processes.

Published
2007

43. Synthesis, characterization and propane metathesis activity of a tantalum-hydride prepared on high surface area 'silica supported zirconium hydroxide'

Author

Franck Rataboul, Christophe Copéret, Laurent Lefort, Jean Thivolle-Cazat, Aimery De Mallmann, Jean-Marie Basset, IRCELYON-C'Durable (CDURABLE), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-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), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Cognitique (ENSC), and Institut Polytechnique de Bordeaux

Subjects
Materials science, 010405 organic chemistry, Hydride, Inorganic chemistry, Tantalum, chemistry.chemical_element, 010402 general chemistry, Metathesis, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Propane, Salt metathesis reaction, [CHIM]Chemical Sciences, Zirconium hydroxide, Organometallic chemistry, ComputingMilieux_MISCELLANEOUS, Nuclear chemistry
Abstract

A new tantalum-hydride supported on zirconium hydroxide [(triple bond SiO)(2)Zr(H)-O-Ta(H)(x)-(OSi triple bond)] (x = 1 or 3) was prepared using surface organometallic chemistry and its catalytic properties in the propane metathesis reaction were assessed showing improved activity and selectivities in comparison to the tantalum-hydride supported on silica.

Published
2007

44. Hybrid-Bridged Silsesquioxane as Recyclable Metathesis Catalyst Derived from a Bis-Silylated Hoveyda-Type Ligand

Author

Joël J. E. Moreau, Roser Pleixats, Xavier Elias, Michel Wong Chi Man, chemistry department universite barcelone, Universitat Autònoma de Barcelona (UAB), 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, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Metathesis, catalyst immobilization • metathesis • organic-inorganic hybrid materials • ruthenium • sol-gel process, 01 natural sciences, Silsesquioxane, 0104 chemical sciences, Catalysis, Tetraethyl orthosilicate, chemistry.chemical_compound, Monomer, chemistry, Polymer chemistry, Salt metathesis reaction, Ring-opening metathesis polymerisation, Hybrid material
Abstract

International audience; The synthesis of a bis-silylated Hoveyda-type monomer is described as well as the preparation of several organic-inorganic hybrid materials derived from it by a sol-gel process (with and without tetraethyl orthosilicate) and by anchoring to MCM-41. The resulting materials were treated with second generation Grubbs' catalyst to generate second generation Hoveyda-Grubbs-type alkylideneruthenium complexes covalently bonded to the silica matrix. These materials are recyclable catalysts for the ring-closing metathesis reaction of dienes and enynes.

Published
2006

45. Substituent effects in tandem ring-closing metathesis reactions of dienynes

Author

François-Didier Boyer, Issam Hanna, Unité de phytopharmacie et médiateurs chimiques, Institut National de la Recherche Agronomique (INRA), Laboratoire de synthèse organique (DCSO), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Alkene, Stereochemistry, Organic Chemistry, Alkyne, General Medicine, Ring (chemistry), 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Grubbs' catalyst, chemistry.chemical_compound, Cycloisomerization, Ring-closing metathesis, chemistry, Salt metathesis reaction, Ring-opening metathesis polymerisation, Physical and Theoretical Chemistry, Acyclic diene metathesis
Abstract

Several dienynes bearing different substituents have been synthesized and subjected to a ring-closing metathesis (RCM) reaction using ruthenium carbene complexes. Dienynes containing a pre-existing ring and a quaternary center attached to the alkyne give the expected tandem metathesis products in high yields. For these substrates, a high selectivity for different ring sizes was achieved by modifying the reactivity of one alkene. In one case, an unusual non-metathetic activity of the second-generation Grubbs catalyst was observed and the cycloisomerization product was obtained as the major product. In the absence of favorable factors, especially when the starting substrates contain hindered alkenes, a long tether chain and/or an ester group on the alkyne part, the tandem process is slowed down or completely impeded. In these cases, dienynes behave like simple enynes and afford initial metathesis products whose further reactions give dimeric compounds.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Published
2006

46. Alkyne Metathesis Catalysts: Scope And Future

Author

André Mortreux, Olivier Coutelier, 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), and 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

Subjects
Alkyne, Homogeneous catalysis, 010402 general chemistry, Metathesis, 01 natural sciences, Catalysis, chemistry.chemical_compound, Deprotonation, Salt metathesis reaction, Alkyne metathesis, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, chemistry.chemical_classification, Molybdenum, Catalysts, 010405 organic chemistry, Chemistry, Process Chemistry and Technology, General Medicine, [CHIM.CATA]Chemical Sciences/Catalysis, Triple bond, Combinatorial chemistry, 0104 chemical sciences, Tungsten complexes, Polymerization, Organic synthesis, Mechanism
Abstract

This paper presents the evolution of alkyne metathesis since the early discoveries, essentially from the catalyst point of view. It is shown that although well defined carbynes may be useful for this reaction, further work has been made, aimed at the synthesis of new catalysts or catalytic systems, based on molybdenum precursors, associated or not with phenolic co-catalysts. The major objectives have been to obtain more functional groups tolerants catalysts, for their application in organic synthesis, including RCM for further stereoselective hydrogenation of the triple bond in the cycle, as well as for polymerization of aromatic diynes. Some insights into the possible mechanisms are given, and data relevant to the metathesis of terminal alkynes, a still challenging reaction where polymerization is occurring via the formation of deprotonated metallacyclobutadiene, are also presented and discussed.

Published
2006

47. Synthesis of Model BC Bicycles of Taxol Using C10-C11 Ring-Closing Metathesis Strategy

Author

Joëlle Prunet, Louis Ricard, Cong Ma, Stéphanie Schiltz, Laboratoire de synthèse organique (DCSO), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire Hétéroéléments et Coordination (DCPH)

Subjects
cyclization, 010405 organic chemistry, Stereochemistry, Taxol, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Substituent, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), Metathesis, 01 natural sciences, Biochemistry, 0104 chemical sciences, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, Ring-closing metathesis, chemistry, Materials Chemistry, Salt metathesis reaction, metathesis, Physical and Theoretical Chemistry, ruthenium
Abstract

6 pages; International audience; Model BC ring-systems of taxol 23b and 28b, which lack an oxygenated substituent at C7, have been efficiently synthesized. The key step is a ring-closing metathesis (RCM) to form the 8-membered B ring between C10 and C11. Comparison of the metathesis reaction in this route with the RCM used in a previous study with similar substrates is highlighted.

Published
2006

48. Use of the olefin metathesis reaction for highly efficient b-cyclodextrin modification

Author

Fabienne Fache, Bernard Bertino Ghera, Hélène Parrot-Lopez, Janvier, Elisabeth, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Cyclodextrin, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, Organic Chemistry, Synthon, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Biochemistry, Grubbs' catalyst, chemistry.chemical_compound, chemistry, Drug Discovery, Salt metathesis reaction, Nucleophilic substitution, Ring-opening metathesis polymerisation, Organic chemistry, Acyclic diene metathesis
Abstract

A series of novel primary face mono-substituted β-cyclodextrin derivatives have been synthesised using the olefin metathesis reaction. Mono-6-allylamino-6-deoxy-β-cyclodextrin easily synthesised by nucleophilic substitution of mono-6-tosyl-β-cyclodextrin is the key synthon in the preparation of cyclodextrin derivatives mono-functionalised at the primary face by alkyl, aryl or perfluoroalkyl groups using Grubbs catalyst. In the cases of vinylbenzene and 1H,1H,2H-perfluoro-1-octene, the metathesis reactions yield with 95% stereoselectivity of the E -isomer.

Published
2006

49. Unexpected dehydrogenation products in the furan series arising from ruthenium-catalyzed 4-oxo-1,6-enyne metathesis

Author

Bernard Bodo, Laurent Evanno, Bastien Nay, Laboratoire de chimie et biochimie des substances naturelles, and Centre National de la Recherche Scientifique (CNRS)-Muséum national d'Histoire naturelle (MNHN)

Subjects
Organic Chemistry, chemistry.chemical_element, General Medicine, Metathesis, Enyne metathesis, Catalysis, Ruthenium, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biomolecules [q-bio.BM], chemistry.chemical_compound, chemistry, Furan, Salt metathesis reaction, Ring-opening metathesis polymerisation, Organic chemistry, Dehydrogenation, Acyclic diene metathesis
Abstract

Metathesis of 4‐oxo‐1,6‐enynes afforded the usual dihydrofuran products accompanied for the first time by unexpected side products identified as the corresponding furans. It probably arose from ruthenium‐catalyzed dehydrogenation of dihydrofurans in the metathesis reaction mixture.

Published
2005

50. Application of Olefin Cross-Metathesis to the Synthesis of Biologically Active Natural Products

Author

Joëlle Prunet, Laboratoire de synthèse organique (DCSO), and École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Macrocyclic Compounds, natural products, Molecular Conformation, review, Alkenes, 010402 general chemistry, Metathesis, 01 natural sciences, Catalysis, Ruthenium, 03 medical and health sciences, 0302 clinical medicine, Heterocyclic Compounds, Drug Discovery, Salt metathesis reaction, Organic chemistry, 030304 developmental biology, Molybdenum, Biological Products, 0303 health sciences, Olefin fiber, Tandem, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Final product, cross-metathesis, Stereoisomerism, General Medicine, Combinatorial chemistry, 0104 chemical sciences, Cyclization, 030220 oncology & carcinogenesis
Abstract

19 pages Merci a Bentam Science Publishers Ltd. d'accepter le dépôt en archives ouvertes; An overview of the use of olefin cross-metathesis in the synthesis of biologically active natural products is presented. The diverse examples are organized according to the outcome of the olefin constructed by the cross-metathesis reaction: this olefin can be either present in the final product, reduced, engaged in other transformations, or involved in tandem processes.

Published
2005

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