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1. Ecodesigned Formulations with Tomato Pomace Extracts

Author

Aya Jamaleddine, Martine Urrutigoïty, Jalloul Bouajila, Othmane Merah, Philippe Evon, and Pascale de Caro

Subjects
tomato pomace, ecoextraction, bioactive molecules, formulation, ecodesign, Chemistry, QD1-999
Abstract

Tomato pomace (TP) has previously been identified as a coproduct that is rich in bioactive molecules, with potential beneficial effects for health. For tomato pomace that is composed of the skin, seeds and fibers, the challenge is to recover the molecules of interest trapped in the biopolymers. The use of deep eutectic solvents to extract metabolites from vegetable materials could present some advantages. Four natural deep eutectic solvents (NaDESs) were synthesized and characterized by infrared spectroscopy, thermogravimetry (TG) and differential scanning calorimetry (DSC). The TP was treated by maceration at moderate temperatures with the NaDESs. We identified 39 extracted molecules by HPLC–DAD, which revealed an abundance of hydroxy/methoxy flavones, flavanols, flavonols, phenolic acids, carotenoids and tannins, as well as a certain selectivity in the extracted molecules. Four cosmetic formulations that included the NaDESs were prepared. The NaDESs showed film-forming properties, which were harnessed for the final formulations, thanks to their biocompatibilities. Finally, the coupling of the extraction and formulation is a way to preserve the quality of the extracts and prepare ecodesigned formulations.

Published
2022
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2. Amaranth Oilseed Composition and Cosmetic Applications

Author

Bouchra Sayed-Ahmad, Martine Urrutigoïty, Akram Hijazi, Zeinab Saad, Muriel Cerny, Philippe Evon, Thierry Talou, and Othmane Merah

Subjects
Amaranth oil, squalene, squalane, catalytic hydrogenation, moisturizing cream, Physics, QC1-999, Chemistry, QD1-999
Abstract

Amaranth (Amaranthus cruentus) is a possible alternative to high-nutritional-value crops. Amaranth seeds are considered to be one of the few sources of phytosqualene (up to 8%). The use of squalene and its hydrogenated form squalane in skincare formulations has been steadily increasing, and the demand for these compounds is expected to rise continuously. The aim of this study was to investigate the amaranth oilseed as a potential ingredient for cosmetic applications. First, an experimental design and optimization were carried out in order to obtain amaranth oil rich in squalane instead of squalene through catalytic hydrogenation. Under the optimal conditions, the resulting oil was fully hydrogenated, with higher stability, and more suitable for cosmetic uses. Furthermore, the effect of the addition of amaranth oil and squalane on the rheological and sensory characteristics of moisturizing cream formulations was assessed. As expected, higher contents of oil and polyunsaturated fatty acids were obtained by supercritical CO2 extraction, and were used for the next step of the experiment. Optimization of the experimental conditions resulted in fully hydrogenated amaranth oil, with higher stability and rich in squalane. Better quality of moisturizing cream formulations was achieved when W/O formulations were enriched with 2% oil, or by adding 1% oil and 1% squalane. The formulation rich in squalane showed a better overall quality compared to other formulations.

Published
2022
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3. Synthesis and antibacterial activity of new 1,2,3-triazolylmethyl-2H-1,4-benzothiazin-3(4H)-one derivatives

Author

Mohamed Ellouz, Nada Kheira Sebbar, Ismail Fichtali, Younes Ouzidan, Zakaria Mennane, Reda Charof, Joel T. Mague, Martine Urrutigoïty, and El Mokhtar Essassi

Subjects
1,2,3-Triazole, 1,4-Benzothiazine, Antimicrobial activity, Cycloaddition, Spectroscopic methods, Chemistry, QD1-999
Abstract

Abstract Background A novel series of 1,2,3-triazole derivatives containing 1,4-benzothiazin-3-one ring (7a–9a, 7b–9b), (10a–12a, 10b–12b) and (13–15) were synthesized by 1,3-dipolar cycloaddition reactions of azides α-d-galactopyranoside azide F, 2,3,4,6-tetra-O-acetyl-(d)-glucopyranosyl azide G and methyl-N-benzoyl-α-azidoglycinate H with compounds 4–6. Findings Initially, the reactions were conducted under thermal conditions in ethanol. The reaction leads, each time, to the formation of two regioisomers: (Schemes 2, 3) with yields of 17 to 21% for 1,5-disubstituted 1,2,3-triazole-regioisomers (7b–12b) and yields ranging from 61 to 65% for the 1,4-disubstituted regioisomers (7a–12a). In order to report an unequivocal synthesis of the 1,4-regioisomers and confirm the structures of the two regioisomers obtained in thermal conditions (Huisgen reactions), the method click chemistry (Copper-Catalyzed Azide-Alkyne Cycloaddition) has been used. Conclusions The newly synthesized compounds using cycloaddition reactions were evaluated in vitro for their antibacterial activities against some Gram positive and Gram negative microbial strains. Among the compounds tested, the compound 8a showed excellent antibacterial activities against PA ATCC and Acin ESBL (MIC = 31.2 μg/ml).

Published
2018
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4. Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Author

Pascale de Caro, Matthieu Bandres, Martine Urrutigoïty, Christine Cecutti, and Sophie Thiebaud-Roux

Subjects
glycerol, glycerol carbonate, transcarbonatation, plasticizer, green chemistry, Chemistry, QD1-999
Abstract

The state of the art on the glycerol carbonate (GC) synthesis has been updated since the last published reviews in 2012, 2013, and 2016. Three types of reactions continue to be studied: glycerolysis of urea, transcarbonation of DMC, DEC, or cyclic carbonates with glycerol and reaction using CO2. Among these different routes, DMC and glycerol were selected as the raw materials for the GC synthesis in this work since the transcarbonation from these green reagents leads to high yields and selectivities, using mild conditions including a less energy consuming GC separation process. Catalytic conditions using Na2CO3 seem to be a good compromise to achieve a high yield of GC, leading to an easier purification step without GC distillation. Mild temperatures for the reaction (73–78°C) as well as a low waste amount confirmed by the E-factor calculation, are in favor of controlled costs. Plasticizing properties of synthesized GC were compared to the behaviors of a commercial plasticizer and natural dialkyl carbonates, for a colorless nail polish formulation. The resulting films subjected to mechanical and thermal stresses (DMA and Persoz pendulum) showed the high plasticizing effect of GC toward nitrocellulose based films, probably due to hydrogen bond interactions between GC and nitrocellulose. The GC efficiency gives the possibility to decrease the content of the plasticizer in the formulation. Glycerol carbonate can be thus considered as a biobased ingredient abiding by the green chemistry concepts, and safe enough to be used in an ecodesigned nail polish formulation.

Published
2019
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5. Avances en la cicloisomerización de eninas catalizada por metales de transición

Author

Ariadna Fuente-Hernández, Odile Dechy-Cabaret, Martine Urrutigoïty, Philippe Kalck, José Alberto Ruiz-García, and Ulises Jáuregui-Haza

Subjects
Chemistry, QD1-999, Science
Abstract

Las eninas son moléculas cuya estructura implica al menos un doble y un triple enlace espaciados o sustituidos o ambos. Estas insaturaciones pueden estar separadas por un heteroátomo. La reactividad de las eninas permite prever el desarrollo de nuevas moléculas con interés para la química fina y farmacéutica. Las reacciones de cicloisomerización de 1,n-eninas catalizadas por metales de transición surgen conceptual y químicamente como procesos muy atractivos debido a que contribuyen a la búsqueda de economía atómica y permiten el descubrimiento de nuevas reacciones y productos. A mediados de los años ochentas, a partir de los estudios pioneros del grupo de Barry Trost con el empleo de paladio, se identifican otros metales como catalizadores para los reordenamientos de los esqueletos de las 1,n-eninas, cuyo comportamiento puede estar influenciado por la presencia de otros grupos funcionales como alcoholes, aldehídos, éteres, alquenos o alquinos. Por otro lado, la creciente demanda de compuestos ópticamente activos ha activado los estudios de reacciones asimétricas catalizadas por metales, en las cuales el ligando quiral desempeña un papel fundamental. Un abundante grupo de moléculas ópticamente activas encontradas en la Naturaleza contienen una funcionalización elevada de carbonos y heterociclos. Estos importantes aspectos estructurales son con frecuencia absolutamente esenciales para la actividad biológica y la función. Existe un gran número de ligandos que ayudan a inducir asimetría en diversas reacciones químicas. Esta revisión analiza las principales contribuciones en este campo de la catálisis y los mecanismos de reacción de la cicloisomerización de eninas catalizada por rodio, platino y oro.

Published
2010

6. Transition‐Metal‐Catalyzed Chiral Amines Synthesis

Author

Philippe Kalck, Anton Cunillera, Carmen Claver, Martine Urrutigoïty, Cyril Godard, Departament de Química Física i Inorganica, Universitat Rovira i Virgili, Universitat Rovira i Virgili, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Alfredo Ricci, and Luca Bernardi

Subjects
Asymmetric hydroaminoalkylation, 010405 organic chemistry, Chemistry, Asymmetric hydroamination, 010402 general chemistry, Hydroaminomethylation, 01 natural sciences, 0104 chemical sciences, Catalysis, Metal-catalyzed reactions, Transition metal, Early metal to noble metal catalysts, Polymer chemistry, Asymmetric reductive amination, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chiral amines
Abstract

International audience; Chiral amines can be synthesized with high yields and enantioselectivities from abundant organic substrates using transition metal catalytic systems containing most of the time an appropriate chiral bidentate ligand. Reductive amination starts from ketones, hydroamination from alkenes, or alkynes in an inter- or intramolecular mode. In the hydroaminoalkylation reaction, a C–H function in α-position with regard to the nitrogen is activated and forms a new C–C bond. In the hydroaminomethylation, a one-pot carbonylation reaction, the olefin reacts with CO/H2 and amine. Complexes chiral-only-at-metal begin to be efficient to perform the photocatalytic chiral amination under mild conditions. Many recent trends are focused onto first-line transition metals. The major difficulties lie in the synthesis of chiral ligands and the design of a suitable coordination sphere.

Published
2021

7. BF3·OEt2-Catalyzed Rearrangement of Epoxy-Himachalenes: Access to New Biosourced N-Acetamide-Based Himachalenes

Author

Mustapha Ait El Had, Abdelouahd Oukhrib, Martine Urrutigoïty, Ahmed Benharref, Moha Taourirte, Mohamed I. Zaki, Faculté des Sciences Semlalia [Marrakech], Université Cadi Ayyad [Marrakech] (UCA), Laboratoire de Chimie Bioorganique et Macromoléculaire - Faculté des Sciences et Techniques (LCBM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Sesquiterpene, 010405 organic chemistry, Chemistry, Organic Chemistry, Himachalene, 010403 inorganic & nuclear chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Catalysis, Solvent, chemistry.chemical_compound, law, Reagent, Lewis acids, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, N-acetamides, Atlas cedar, Acetonitrile, Essential oil, Acetamide
Abstract

Biosourced N-acetamide-based himachalenes were synthesized by Lewis acid catalyzed rearrangement of epoxy-himachalene derived from α-cis- and β-himachalenes, the main component of essential oil of Atlas cedar (Cedrus atlantica). Several new chiral polycyclic N-acetamide compounds were obtained with different selectivities depending on the acid used. Among the Lewis acids used, BF3·OEt2 under catalytic and mild conditions is efficient and selective affording the formation of chiral N-acetamides in good yields. Otherwise, using acetonitrile as solvent and reagent was proved as an efficient tool giving access to new N-acetamide-based himachalenes. A mechanism to explain the formation of the different compounds observed in the reaction mixture has also been proposed.

Published
2020

8. Efficient synthesis of chiral γ-aminobutyric esters via direct rhodium-catalysed enantioselective hydroaminomethylation of acrylates

Author

Carmen Claver, Miriam Díaz de los Bernardos, Aurora Ruiz, Martine Urrutigoïty, Anton Cunillera, Cyril Godard, Departament de Química Física i Inorganica, Universitat Rovira i Virgili, Universitat Rovira i Virgili, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Reaction mechanism, 010405 organic chemistry, Chemistry, Ligand, Intermolecular force, Enantioselective synthesis, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Rhodium, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; The successful rhodium catalysed asymmetric intermolecular hydroaminomethylation (HAM) of alkenes using a single catalyst bearing the (R,R)-QuinoxP* ligand is reported. The HAM of α-alkyl acrylates is revealed to be an efficient tool for the regio- and enantioselective synthesis of γ-amino esters with ees up to 86%. HPNMR experiments provided insights into the reaction mechanism.

Published
2020

9. Modeling of Ethylene Glycol Production from Glucose in a Semi‐Continuous Reactor

Author

Ghislain Irakoze, François Jérôme, Yolande Pérès, Michel Delmas, Patrick Cognet, Karine De Oliveira Vigier, Martine Urrutigoïty, Carlos Murillo, Laboratoire de Génie Chimique (LGC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), 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)-Centre National de la Recherche Scientifique (CNRS), and INCREASE CNRS federation

Subjects
Process modeling, 010405 organic chemistry, Chemistry, General Chemical Engineering, Continuous reactor, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Industrial and Manufacturing Engineering, 0104 chemical sciences, Catalysis, modelling, chemistry.chemical_compound, Chemical engineering, semi-continuous reaction, reaction kinetics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, glucose, 0210 nano-technology, Ethylene glycol
Abstract

International audience; A numerical study describes the catalytic conversion of glucose into ethylene glycol (EG) in a semi-batch reactor. This analysis couples a set of power law models (homogeneous reactions) and Langmuir-Hinshelwood-Hougen-Watson (LHHW) equations (hydrogenations). For this purpose, the kinetic parameters of the LHHW expressions are estimated for the reaction conditions. Then, the kinetic model evaluates the influence of the H2 pressure and the catalyst concentrations on the selectivity. The results indicate that the EG yield is increased by setting the temperature and the H2 pressure. In this manner, the process reduces the hexitols and methane production and increases the EG yield. The originality of the work is based on the influence of the H2 pressure and the catalyst concentrations in the model.

Published
2020

10. Versatile synthesis of cadalene and iso-cadalene from himachalene mixtures: Evidence and application of unprecedented rearrangements

Author

Mustapha Ait El Had, Abdelouahd Oukhrib, Martine Urrutigoïty, Remi Chauvin, Ahmed Benharref, Mohamed A. Zaki, Laboratoire de Chimie Biomoléculaires, Substances Naturelles et Réactivité, URAC16, Faculté des Sciences Semlalia [Marrakech], Université Cadi Ayyad [Marrakech] (UCA)-Université Cadi Ayyad [Marrakech] (UCA), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Faculté des Sciences, Semlalia, Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Rearrangements, Bicyclic molecule, Cyclohexane, Hydride, Himachalenes, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Yield (chemistry), Dihydrocurcumene, Organic chemistry, Aromatic reactivity, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cadalenes, 0210 nano-technology, Selectivity, Cadalene, Bond cleavage, Dichloromethane
Abstract

International audience; From a mixture of α-, β- and γ-himachalenes extracted from waste wood of Atlas cedar (Cedrus atlantica), cadalene (1,6-dimethyl-4-isopropylnaphthalene) and iso-cadalene (1,6-dimethyl-3-isopropylnaphthalene) were produced in two steps with up to 71% ± 5% yield through the ar-himachalene intermediate using I2 and/or AlCl3 as reagents. The selectivity is shown to sharply depend on the operating conditions: while I2/AlCl3 in dichloromethane promotes the formation of cadalene, the formation of iso-cadalene is favored in the presence of AlCl3 in cyclohexane. The bicyclic aromatic compounds were thus obtained through unique rearrangements involving sequential CC bond cleavage/formation and hydride transfer processes. In the absence of AlCl3 or I2, dihydrocurcumene was also found to be formed with up to 70% selectivity. A tentative mechanism is proposed and discussed.

Published
2020

11. Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes

Author

Philippe Kalck, Martine Urrutigoïty, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Alkene, Imine, Regioselectivity, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Enamine, chemistry.chemical_compound, Atom economy, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chemoselectivity, Hydroformylation
Abstract

International audience; In the context of atom economy and low environmental impact, synthesis of amines by an efficient catalytic process is of great importance to produce these building blocks for fine chemical industry. The one-pot hydroaminomethylation of alkenes is a tandem reaction which involves three successive steps under CO/H2 pressure to perform the catalyzed hydroformylation of the alkene into the corresponding aldehyde followed by its condensation with a N–H function and the catalyzed hydrogenation of the imine/enamine intermediate into the corresponding saturated amine. Rhodium and more recently ruthenium complexes have been designed to combine high conversions of the reactants and chemoselectivity in the expected amines with high regioselectivity in either the linear or the branched amine. The coordination sphere of the metal according to the presence of ligands, temperature, CO/H2 partial pressures, and nature of the solvent is essential for complying with these selectivity requirements. The rate of the hydroformylation step needs to be fast with regard to the hydrogenation step. The role of amines in the coordination sphere and water, presumably in the second sphere, on the mechanism requires some more studies. Similarly, the enantioselective synthesis of amine is not yet achieved directly and interrupted processes or use of asymmetric organo-catalyzed reductive amination are efficient synthetic ways for producing chiral amines. The separation of the catalyst from the organic products by biphasic or (semi-) heterogeneized systems and its recycling have been demonstrated in many cases. The present review provides a report of the state of the art in this autotandem hydroaminomethylation catalysis and should open prospects in the design of less expensive and abundant metal complexes for reaching at low cost similar and even superior performances.

Published
2018

12. Recent Progress in Synthesis of Glycerol Carbonate and Evaluation of Its Plasticizing Properties

Author

Martine Urrutigoïty, Sophie Thiebaud-Roux, Matthieu Bandres, Christine Cecutti, Pascale De Caro, Chimie Agro-Industrielle (CAI), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques-Institut National de la Recherche Agronomique (INRA), Laboratoire de chimie de coordination (LCC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Institut National de la Recherche Agronomique - INRA (FRANCE), Institut National Polytechnique de Toulouse - INPT (FRANCE), Laboratoire de Chimie Agro-Industrielle (LCA), Institut National de la Recherche Agronomique (INRA)-Ecole Nationale Supérieure de Chimie de Toulouse, Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Recherche Agronomique (INRA)-Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques (ENSIACET), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), and DURLIN

Subjects
Green chemistry, 02 engineering and technology, glycerol, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, lcsh:Chemistry, chemistry.chemical_compound, Transcarbonatation, law, Glycerolysis, Plasticizer, Glycerol, Matériaux (Chimie), Distillation, Original Research, glycerol carbonate, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Separation process, Chemistry, lcsh:QD1-999, chemistry, Chemical engineering, Material chemistry, Yield (chemistry), transcarbonatation, plasticizer, green chemistry, Glycerol carbonate (GC), 0210 nano-technology, Sciences agricoles
Abstract

International audience; The state of the art on the glycerol carbonate (GC) synthesis has been updated since the last published reviews in 2012, 2013, and 2016. Three types of reactions continue to be studied: glycerolysis of urea, transcarbonation of DMC, DEC, or cyclic carbonates with glycerol and reaction using CO2. Among these different routes, DMC and glycerol were selected as the raw materials for the GC synthesis in this work since the transcarbonation from these green reagents leads to high yields and selectivities, using mild conditions including a less energy consuming GC separation process. Catalytic conditions using Na2CO3 seem to be a good compromise to achieve a high yield of GC, leading to an easier purification step without GC distillation. Mild temperatures for the reaction (73–78°C) as well as a low waste amount confirmed by the E-factor calculation, are in favor of controlled costs. Plasticizing properties of synthesized GC were compared to the behaviors of a commercial plasticizer and natural dialkyl carbonates, for a colorless nail polish formulation. The resulting films subjected to mechanical and thermal stresses (DMA and Persoz pendulum) showed the high plasticizing effect of GC toward nitrocellulose based films, probably due to hydrogen bond interactions between GC and nitrocellulose. The GC efficiency gives the possibility to decrease the content of the plasticizer in the formulation. Glycerol carbonate can be thus considered as a biobased ingredient abiding by the green chemistry concepts, and safe enough to be used in an ecodesigned nail polish formulation.

Published
2019

13. Synthesis and antibacterial activity of new 1,2,3-triazolylmethyl-2H-1,4-benzothiazin-3(4H)-one derivatives

Author

Joel T. Mague, El Mokhtar Essassi, Reda Charof, Younes Ouzidan, Martine Urrutigoïty, I. Fichtali, Mohamed Ellouz, Nada Kheira Sebbar, Zakaria Mennane, Faculté des sciences [Rabat], Université Mohammed V de Rabat [Agdal], Université Sidi Mohamed Ben Abdellah (USMBA), Institut National d'Hygiène [Maroc], Tulane University, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Moroccan Foundation for Advanced Science, Innovation and Research (MASCIR)

Subjects
1,2,3-Triazole, 4-Benzothiazine, Antimicrobial activity, 010402 general chemistry, 3-Triazole, 01 natural sciences, Medicinal chemistry, chemistry.chemical_compound, Structural isomer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, QD1-999, Cycloaddition, Gram, Ethanol, 010405 organic chemistry, General Chemistry, 0104 chemical sciences, Chemistry, chemistry, Click chemistry, Spectroscopic methods, Azide, 1,4-Benzothiazine, Antibacterial activity, Research Article
Abstract

Background A novel series of 1,2,3-triazole derivatives containing 1,4-benzothiazin-3-one ring (7a–9a, 7b–9b), (10a–12a, 10b–12b) and (13–15) were synthesized by 1,3-dipolar cycloaddition reactions of azides α-d-galactopyranoside azide F, 2,3,4,6-tetra-O-acetyl-(d)-glucopyranosyl azide G and methyl-N-benzoyl-α-azidoglycinate H with compounds 4–6. Findings Initially, the reactions were conducted under thermal conditions in ethanol. The reaction leads, each time, to the formation of two regioisomers: (Schemes 2, 3) with yields of 17 to 21% for 1,5-disubstituted 1,2,3-triazole-regioisomers (7b–12b) and yields ranging from 61 to 65% for the 1,4-disubstituted regioisomers (7a–12a). In order to report an unequivocal synthesis of the 1,4-regioisomers and confirm the structures of the two regioisomers obtained in thermal conditions (Huisgen reactions), the method click chemistry (Copper-Catalyzed Azide-Alkyne Cycloaddition) has been used. Conclusions The newly synthesized compounds using cycloaddition reactions were evaluated in vitro for their antibacterial activities against some Gram positive and Gram negative microbial strains. Among the compounds tested, the compound 8a showed excellent antibacterial activities against PA ATCC and Acin ESBL (MIC = 31.2 μg/ml).

Published
2018

14. Syntheses, crystal structures, spectroscopic characterizations, DFT calculations, hirshfeld surface analyses and monte carlo simulations of novel long-chain alkyl-substituted 1,4-benzothiazine derivatives

Author

Joel T. Mague, Tuncer Hökelek, Brahim El Ibrahimi, El Mokhtar Essassi, Noureddine Hamou Ahabchane, El Hassane Anouar, Martine Urrutigoïty, Brahim Hni, Mohamed Ellouz, Nada Kheira Sebbar, Université Mohammed V de Rabat [Agdal], Université Ibn Zohr [Agadir], Prince Sattam Bin Abdul-Aziz University (PSAU), Hacettepe University = Hacettepe Üniversitesi, Tulane University, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
4-dihydro-2H-1, Monte Carlo method, chemistry.chemical_element, Crystal structure, Benzothiazine, Alkylation, 010402 general chemistry, DFT, 01 natural sciences, Analytical Chemistry, X-ray, Inorganic Chemistry, chemistry.chemical_compound, Computational chemistry, Hirshfeld surface analysis, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Spectroscopy, Alkyl, 4-benzothiazin-3-one, chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Nuclear magnetic resonance spectroscopy, Copper, 0104 chemical sciences, chemistry, Corrosion inhibitor, NMR characterization, Density functional theory
Abstract

International audience; In this work, three novel long-chain alkyl substituted 1,4-benzothiazine derivatives have been synthesized by alkylation reactions under phase transfer catalysis conditions. The obtained compounds (4, 5 and 6) obtained were characterized using 1H- and 13C- NMR spectroscopy and X-ray. Their molecular and crystal structures have been determined by single-crystal X-ray diffraction techniques. The experimental data, were compared with the predicted ones spectral data were also obtained using density functional theory (DFT) at the B3LYP/6-31G(d,p) level of theory. In addition, the closest contacts between the active atoms of the compounds were identified through Hirshfeld surface analyses. According to Monte Carlo simulations, the new compounds can act as good corrosion inhibitors for iron and as moderate ones for copper and aluminum metals.

Published
2020

15. Syntheses of N-substituted benzimidazolone derivatives: DFT calculations, Hirshfeld surface analysis, molecular docking studies and antibacterial activities

Author

Nabil Al-Zaqri, Lhoussaine El Ghayati, Yassir Filali Baba, Ahmed Talbaoui, El Mokhtar Essassi, Asmaa Saber, Martine Urrutigoïty, Yusuf Sert, Nada Kheira Sebbar, Tuncer Hökelek, Joel T. Mague, Université Mohammed V de Rabat [Agdal], Université Ibn Zohr [Agadir], Bozok University, Yozgat, King Saud University [Riyadh] (KSU), Hacettepe University = Hacettepe Üniversitesi, Tulane University, Université de Fez, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Crystal structure, Hirshfeld surface, Organic Chemistry, 010402 general chemistry, DFT, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Inorganic Chemistry, Minimum inhibitory concentration, Benzimidazolone, Computational chemistry, Molecular docking, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Density functional theory, Antibacterial activity, Spectral data, Single crystal, Spectroscopy
Abstract

International audience; New benzimidazolone derivatives (2–5) were synthesized and characterized using NMR and single crystal X-ray diffraction techniques. Along with the experimental data, the predicted spectral data were also obtained using density functional theory (DFT) at the B3LYP/6-31G(d,p) level of theory. In addition, the closest contacts between the active atoms of the compounds were identified through Hirshfeld surface analyses, molecular docking studies, and DFT calculations. The antibacterial activities of derivatives (2–5) against gram-positive and gram-negative microbial strains, such as Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa were also evaluated, and the results obtained showed the antibacterial activities of derivatives (2–5) using a minimum inhibitory concentration (MIC) assay.

Published
2020

16. Phospholes as efficient ancillaries for the rhodium-catalyzed hydroformylation and hydroaminomethylation of estragole

Author

Elena V. Gusevskaya, Maryse Gouygou, Martine Urrutigoïty, Sabrina N. Carvalho, Jamal El Karroumi, Eduardo N. dos Santos, Matheus F. Duarte, Kelley C.B. Oliveira, Federal University of Minas Gerais (UFMG), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie des substances naturelles, Université Cadi Ayyad [Marrakech] (UCA), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
chemistry.chemical_classification, Alkene, Process Chemistry and Technology, chemistry.chemical_element, Reductive amination, Catalysis, Enamine, Rhodium, chemistry.chemical_compound, chemistry, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Triphenylphosphine, Chemoselectivity, Hydroformylation, Phosphine
Abstract

International audience; The hydroaminomethylation (HAM) of estragole, a bio-renewable starting material, with di-n-butylamine was studied for the first time resulting in three novel amines. The process consists of the alkene hydroformylation followed by the in situ reductive amination of primarily formed aldehydes. In order to control chemo- and regioselectivities, three classes of phosphorus(III) compounds were employed as ancillaries for rhodium(I) catalysts: phosphine, phosphites and phospholes. Phosphole-promoted systems have showed the best overall performance, being more selective in the hydrofomylation step than non-promoted or phosphite-promoted systems, as well as more efficient in the reductive amination step than the standard triphenylphosphine based system. It has been found that both the double bond isomerization (a concurrent reaction) and the enamine hydrogenation (the last step in the HAM process) are favored by less electron-donating ligands, with phospholes presenting an excellent compromise to ensure high chemoselectivity and reasonably fast formation of target amines.

Published
2015

17. Chiral bidentate [N,S]-ferrocene ligands based on a thiazoline framework. Synthesis and use in palladium-catalyzed asymmetric allylic alkylation

Author

Maryse Gouygou, José Enrique Barquera-Lozada, E. P. Sanchez-Rodriguez, M. C. Ortega-Alfaro, Ricardo Corona-Sánchez, José G. López-Cortés, Rubén A. Toscano, Martine Urrutigoïty, F. Hochberger-Roa, Instituto de Quı́mica, Universidad Nacional Autónoma de México, Universidad Nacional Autónoma de México (UNAM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, Instituto de Ciencias Nucleares, UNAM, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Denticity, 010405 organic chemistry, Stereochemistry, Thiazoline, chemistry.chemical_element, Oxazoline, Planar chirality, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Tsuji–Trost reaction, chemistry, Ferrocene, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chirality (chemistry), Palladium
Abstract

International audience; An efficient method to obtain chiral 1,2-disubstituted ferrocenyl ligands has been developed. The introduction of planar chirality was accomplished by using 2-thiazoline as an ortho-directing lithiation group, and moreover, these kinds of ligands possess a central chirality from the amino alcohol used in their synthesis. The X-ray analysis and DFT calculations confirmed the diastereoselectivity of ortho-lithiation and the configuration of the planar chirality. The ability of these new bidentate [N,S]-ferrocene ligands to act in Pd-catalyzed asymmetric allylic alkylation has also been demonstrated and compared with their oxazoline counterparts.

Published
2017

18. Water‐Soluble Hydroformylation Catalysis

Author

Martine Urrutigoïty, Philippe Kalck, and Duc Hanh Nguyen

Subjects
Water soluble, Chemistry, Organic chemistry, Hydroformylation, Catalysis
Published
2013

19. Novel phospholyl(diphenylphosphino)methane-ruthenium complexes: unexpected non-assisted cis to trans isomerization of [RuCl2(κ2-P–P′)2]

Author

Martine Urrutigoïty, Thomas Davin, Maryse Gouygou, Sonia Mallet-Ladeira, Jean-Claude Daran, Duc Hanh Nguyen, Laurent Maron, Philippe Kalck, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-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-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT), 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), 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), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Stereochemistry, Ligand, Phosphole, Molecular Conformation, Diastereomer, chemistry.chemical_element, Crystallography, X-Ray, Ligands, 010402 general chemistry, 01 natural sciences, Ruthenium, Methane, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Organophosphorus Compounds, Isomerism, Coordination Complexes, Dimethyl Sulfoxide, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Isomerization
Abstract

International audience; Using the unsymmetrical P–P′ phospholyl(phosphino)methane ligand, complex cis-[RuCl2(κ2-P–P′)2] is easily prepared from [RuCl2(DMSO)4]. The two phosphole-phosphorus atoms lie in the trans position to the two cis-chloro ligands. This complex slowly isomerizes spontaneously at 20 °C to the trans-[RuCl2(κ2-P–P′)2] diastereoisomer where the two phosphole moieties are mutually trans, as well as the two chloro ligands and the two Ph2P moieties. DFT calculations show that this non-classical cis–trans isomerisation process requires a 3 kcal mol−1 energy and involves the decoordination of a phosphole arm.

Published
2013

20. [N,P]-pyrrole PdCl2 complexes catalyzed the formation of dibenzo-α-pyrone and lactam analogues

Author

Maryse Gouygou, M. C. Ortega-Alfaro, Jesus V. Suarez‐Meneses, Abdelhouad Oukhrib, José G. López-Cortés, Jean-Claude Daran, Martine Urrutigoïty, Alejandro Cordero-Vargas, Instituto de Quı́mica, Universidad Nacional Autónoma de México, Universidad Nacional Autónoma de México (UNAM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, and Instituto de Ciencias Nucleares, UNAM

Subjects
010405 organic chemistry, Stereochemistry, Phosphole, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, Pyrone, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Intramolecular force, Lactam, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Palladium, Pyrrole
Abstract

International audience; We herein report the synthesis and catalytic application of a new family of [N\P], ligands based on the pyrrole ring with alpha-phosphine or phosphole units. Their palladium complexes (3a-d) were obtained in very good yields and their catalytic properties were evaluated in the direct intramolecular arylation to obtain both benzopyranones and phenanthridinones. The air stable complex 3a exhibited the best catalytic performance of this series of complexes, using 1 mol% of catalyst in combination with microwaves to promote this reaction.

Published
2016

21. Tandem Rhodium Carbonylation Reactions

Author

Philippe Kalck, Martine Urrutigoïty, Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire de chimie de coordination (LCC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Claver, C.

Subjects
chemistry.chemical_classification, Tandem, 010405 organic chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Aldehyde, Combinatorial chemistry, Chemical synthesis, 0104 chemical sciences, Rhodium, chemistry, Cascade reaction, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbonylation, Hydroformylation
Abstract

International audience; This review presents the recent advances in the rhodium-catalyzed tandem carbonylation reactions involving in the main step the hydroformylation. Such reactions open huge opportunities in synthetic chemistry, since they offer a general efficient strategy to synthesize building blocks for fine chemistry, starting from abundant and low price substrates and avoiding the formation of substantial amounts of by-products. This atom-efficient tandem reaction approach shows that rhodium has a privileged place in the CO chemistry, not only to perform the hydroformylation reaction but also to functionalize the aldehyde function in a one-pot process.

Published
2016

22. Interplay between Cationic and Neutral Species in the Rhodium-Catalyzed Hydroaminomethylation Reaction

Author

Aitor Gual, David McKay, Philippe Kalck, Laurent Maron, Cyril Godard, Chiara Dinoi, Martine Urrutigoïty, Delphine Crozet, Jean-Claude Daran, Carmen Claver, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Departament de Química Física i Inorganica, Universitat Rovira i Virgili, Universitat Rovira i Virgili, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), 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), 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), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Organic Chemistry, Inorganic chemistry, Cationic polymerization, Infrared spectroscopy, chemistry.chemical_element, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Oxidative addition, hydroaminomethylation, Catalysis, 0104 chemical sciences, Rhodium, NMR spectroscopy, Deprotonation, chemistry, density functional calculations, rhodium, coordination chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reactivity (chemistry), Amine gas treating
Abstract

International audience; The reactivity of [Rh(CO)2{(R,R )‐PhBPE}]BF4 (2 ) toward amine, CO and/or H2 was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)3{(R,R )‐PhBPE}]BF4 (4 ) and [Rh(CO)2(NHC5H10){(R,R )‐Ph‐BPE}]BF4 (8 ) were identified. The transformation of 2 into the neutral complex [RhH(CO)2{(R,R )‐PhBPE}] (3 ) under hydroaminomethylation conditions (CO/H2, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)2(CO)2{(R,R )‐PhBPE}]BF4 (6 ), resulting from the oxidative addition of H2 on 2 .

Published
2012

23. Modular Phosphole-Methano-Bridged-Phosphine(Borane) Ligands. Application to Rhodium-Catalyzed Reactions

Author

Jean-Claude Daran, Christine Salomon-Bertrand, Philippe Kalck, Jérôme Bayardon, Sylvain Jugé, Duc Hanh Nguyen, Martine Urrutigoïty, and Maryse Gouygou

Subjects
Organic Chemistry, Phosphole, DABCO, Borane, Medicinal chemistry, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Nucleophile, Electrophile, Nucleophilic substitution, Organic chemistry, Moiety, Physical and Theoretical Chemistry, Phosphine
Abstract

The synthesis of the phospholyl(phosphinoborane)methane air- and moisture-stable hybrid ligands 4a–f, starting from 1-phenylphospholes 1a–d, was performed via P–C bond coupling on the methano bridge. Two strategies were investigated, according to the phospholyl moiety used as a nucleophilic or an electrophilic reagent. In the first pathway, the phospholyl anions react with the easily available (chloromethyl)diphenylphosphine–borane 3 to afford ligands 4a–d in 29–67% isolated yields. In the second pathway, the phospholyl(dicyclohexylphosphinoborane)methane ligands 4e,f were synthesized in 18–23% yields, through a nucleophilic substitution on the cyanophosphole. Removal of the BH3 moiety on 4a–c assisted by DABCO leads to the hybrid phospholyl(diphenylphosphino)methanes 5a–c. Compounds 4 and 5 were fully characterized by multinuclear NMR spectroscopy (1H, 31P, 13C, 11B), mass spectrometry, and elemental analysis, and the X-ray crystal structures of 4a,c and 5a,b have been established. Ligands 5a,b were used...

Published
2012

24. Contrasted effect of CO on the metal-catalyzed cycloisomerization of O-tethered enynes derived from monoterpenes

Author

Ariadna Fuente-Hernàndez, Martine Urrutigoïty, Philippe Kalck, Ulises Jáuregui-Haza, Philippe Costes, and Odile Dechy-Cabaret

Subjects
chemistry.chemical_classification, Enyne, Stereochemistry, Ligand, Alkyne, General Chemistry, Triple bond, Catalysis, Inorganic Chemistry, Metal, Reaction rate, Cycloisomerization, chemistry, visual_art, visual_art.visual_art_medium
Abstract

The CO-bubbling effect in cycloisomerization reactions of enynes derived from monoterpenes has been studied using PtCl2, [Rh2Cl2(CO)4] and AuCl3 as catalytic systems. All the precursors are efficient catalysts for the cycloisomerization of O-tethered enynes. The reaction proceeds through exo-dig and endo-dig pathways, which are consistent with the exclusive coordination of the alkyne triple bond to the metal center. The CO ligand not only increases the reaction rates but also induces significant variations in the two reaction pathways. Notably, this effect is also strongly dependent on the nature of the starting enyne. Copyright © 2011 John Wiley & Sons, Ltd.

Published
2011

25. Recent Advances in Amine Synthesis by Catalytic Hydroaminomethylation of Alkenes

Author

Philippe Kalck, Delphine Crozet, and Martine Urrutigoïty

Subjects
chemistry.chemical_classification, Alkene, Organic Chemistry, Imine, chemistry.chemical_element, Aldehyde, Catalysis, Rhodium, Enamine, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Organic chemistry, Amine gas treating, Physical and Theoretical Chemistry, Carbonylation
Abstract

Carbon–carbon coupling catalyzed by transition metals represents a powerful synthetic method to have an access to organic molecules, especially when they present a significant complexity. The strategy to transform abundant and not expensive reactants into products of pharmaceutical interest by the appropriate catalytic way is of fundamental interest, provided that high conversion rates and selectivities can be gained. During the past decade, considerable progress has been made to transform a simple alkene into an aldehyde by carbonylation, to condense it with an NH function-containing molecule present in the medium, and to hydrogenate the resulting imine or enamine into the relevant amine. Rhodium complexes are able to catalyze this series of reactions and be an efficient synthetic tool to produce rather sophisticated amines in one-pot reactions under mild conditions of pressure and temperature. In the future, the production of various amines required by the industry of fine chemicals looks attractive by means of this catalytic method.

Published
2011

26. N-phosphanylamidine ligands and their catalytic activity in the hydroformylation of 1-octene and styrene

Author

Jennifer Steele, Alain Igau, Laure Vendier, Martine Urrutigoïty, Régis Maura, Philippe Kalck, Stéphanie Bastin, and Damien Arquier

Subjects
Denticity, Dimer, Organic Chemistry, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Biochemistry, Medicinal chemistry, Catalysis, Rhodium, Inorganic Chemistry, Amidine, chemistry.chemical_compound, chemistry, Pyridine, Materials Chemistry, Organic chemistry, Physical and Theoretical Chemistry, Hydroformylation
Abstract

Pyridine-based N-phosphanylamidine ligands i-Pr2N–C(pyr) N–PR2 (R = Ph (3), i-Pr (4)) were synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Mononuclear rhodium complexes 7 and 8 were obtained in one step from the [RhCl(COD)]2 dimer and the monodentate ligands 1 and 2. Their single-crystal X-ray diffraction studies revealed the structural adaptive behavior of the monodentate N-phosphanylamidine ligands 1 and 2 upon k1-P coordination mode in rhodium(I) complexes with the imino nitrogen atom of the amidine function which behaves as a “universal joint”. Compounds 1–4 were evaluated as ligands in the 1-octene and styrene hydroformylation reactions. The results obtained are encouraging and represent the first report on the use of N-phosphanylamidine ligands of the type R″2N–C(R′) N–PR2 in catalytic reactions.

Published
2011

27. Lewis acid- and Bronsted acid-catalyzed stereoselective rearrangement of epoxides derived from himachalenes: access to new chiral polycyclic structures

Author

Martine Urrutigoïty, Eric Manoury, Sandra Parrès-Maynadié, Maryse Gouygou, Abderrahim El Haib, and Ahmed Benharref

Subjects
Reaction conditions, Chemistry, Organic Chemistry, Catalysis, law.invention, Inorganic Chemistry, law, Organic chemistry, Stereoselectivity, Lewis acids and bases, Physical and Theoretical Chemistry, Brønsted–Lowry acid–base theory, Essential oil
Abstract

The acid-catalyzed rearrangement of two enantiomerically pure epoxides derived from sesquiterpernic himachalenes, which are the main components of the essential oil of the Atlas cedar, has been studied using various Lewis and Bronsted acids. Several new polycyclic compounds have been obtained with different selectivities depending upon the catalysts used and the reaction conditions, and were fully characterized by spectroscopic methods. Mechanisms to explain the formation of the different compounds observed in the reaction mixture have also been proposed.

Published
2011

28. Highly catalyst-dependent cycloisomerisation of an O-tethered enyne derived from nerol

Author

Philippe Costes, J.A. Ruiz-García, Ulises Jáuregui-Haza, Philippe Kalck, Martine Urrutigoïty, Odile Dechy-Cabaret, and Ariadna Fuente-Hernández

Subjects
Enyne, Process Chemistry and Technology, chemistry.chemical_element, Homogeneous catalysis, General Chemistry, Medicinal chemistry, Catalysis, Cyclopropane, Rhodium, chemistry.chemical_compound, chemistry, Nerol, Organic chemistry, Selectivity, Platinum
Abstract

The cycloisomerisation of an O-tethered enyne derived from nerol has been studied using various catalytic systems such as PtCl 2 , AuCl 3 , {[AuCl(PPh 3 )]/AgPF 6 } and [Rh 2 Cl 2 (CO) 4 ]. Whatever the catalyst used, formal Alder-ene 1,4-dienes were obtained as major products along with cyclopropane and 1,3-diene derivatives, indicating the crucial influence of the structure of the enyne substrate on the course of the reaction. Differences in terms of activity and selectivity nevertheless appeared when moving from Rh- or Pt-based catalysts to Au(I)-based catalysts: mechanistic pathways are proposed to explain these observations.

Published
2010

29. Probing the stereo-electronic properties of cationic rhodium complexes bearing chiral diphosphine ligands by 103 Rh NMR

Author

Lionel Perrin, Odile Dechy-Cabaret, Laurent Maron, Amandine Fabrello, Philippe Kalck, Martine Urrutigoïty, and Chiara Dinoi

Subjects
Steric effects, Stereochemistry, Cationic polymerization, chemistry.chemical_element, General Chemistry, Ring (chemistry), Rhodium, chemistry.chemical_compound, Crystallography, chemistry, Diphosphines, General Materials Science, Catalytic hydrogenation, BINAP, Electronic properties
Abstract

103Rh NMR represents a powerful tool to assess the global electronic and steric contribution of diphosphine ligands on [Rh(COD)(diphosphine)]+ complexes. In the case of DIOP, BINAP and MeDUPHOS, this approach proved to be more informative than classical CO-stretching frequency measurements. After validation, this method has been extended to a set of seven diphosphines. 103Rh NMR measurements on [Rh(COD)(diphosphine)]PF6 lead to the following order of donor properties: dppe > MeBPE > MeDUPHOS > dppb > DIOP > BINAP > Tol-BINAP. This trend has been validated by DFT in the case of DIOP, BINAP and MeDUPHOS. In conjunction, 31P NMR chemical shift has been shown to reflect the ring constraints of the Rh-diphosphine scaffold. This contribution is a step towards a mechanistic investigation of the catalytic hydrogenation of unsaturated substrates by 103Rh NMR and DFT. Copyright © 2010 John Wiley & Sons, Ltd.

Published
2010

30. Molecular rearrangement of epoxide derived from sesquiterpenes by Lewis acid catalysis

Author

Maryse Gouygou, Abderrahim El Haib, Ahmed Benharref, Sandra Parrès-Maynadié, Martine Urrutigoïty, Jean-Claude Daran, and Eric Manoury

Subjects
chemistry.chemical_classification, Ketone, 010405 organic chemistry, Organic Chemistry, Epoxide, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Lewis acid catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Yield (chemistry), Organic chemistry, Physical and Theoretical Chemistry, Molecular rearrangement
Abstract

The molecular rearrangement under mild conditions of two epoxides derived from the sesquiterpenic himachalenes has been studied using BF 3 ·Et 2 O as the Lewis acid catalyst. Both reactions are efficient and selective affording in each case one new enantiomerically pure ketone isolated in good yield. Their structures have been fully characterized by spectroscopic methods. Mechanisms for the BF 3 -catalyzed reactions are proposed.

Published
2010

31. Mechanistic analysis of the transition metal-catalyzed hydrogenation of imines and functionalized enamines

Author

Philippe Kalck, Alice Bachelier, Martine Urrutigoïty, and Amandine Fabrello

Subjects
Ligand, Chemistry, Shvo catalyst, Hydride, Asymmetric hydrogenation, Noyori asymmetric hydrogenation, Photochemistry, Oxidative addition, Asymmetric induction, Reductive elimination, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Physical and Theoretical Chemistry
Abstract

The asymmetric hydrogenation of prochiral imines has been mainly studied on cationic rhodium or iridium complexes and involves the coordination of the nitrogen atom on the metal centre. Oxidative addition of dihydrogen followed by one hydride transfer onto the carbon atom produces a σ-bonded nitrogen-metal intermediate from which reductive elimination occurs with the second hydride to produce the amine. From all these reactivity studies we propose that in an early step a hydrogen atom transfer could occur on the nitrogen atom to generate an iminium species which coordinates the metal centre through the C N double bond. The Shvo catalyst, an active neutral ruthenium(II) complex, presents the particularity to transfer almost simultaneously a proton from the hydroxycyclopentadienyl ligand and a hydride bonded to the metal center. In this case too, we suggest the first proton transfer generates an iminium species. Morever, a few titanium complexes have been shown to catalyze the hydrogenation of imines. Concerning enamines, literature is rather scarce on catalytic success. On the contrary, many studies focused on hydrogenation of enamides, which represent functionalized enamines, and enantiomeric excesses very close to 100% have been obtained. Extensive studies of the effect of the (chiraldiphosphine)Rh + framework on the asymmetric induction have shown that several reversible steps can occur related to the oxidative addition of dihydrogen before or after the coordination of the enamide; the irreversible step directly connected to the asymmetric induction is the formation of the chiral alkyl-rhodium species.

Published
2010

32. First Dibenzophospholyl(diphenylphosphino)methane−Borane Hybrid P−(η2-BH3) Ligand: Synthesis and Rhodium(I) Complex

Author

Duc Hanh Nguyen, Hugo Laureano, Martine Urrutigoïty, Sylvain Jugé, Philippe Kalck, Jean-Claude Daran, Yannick Coppel, and Maryse Gouygou

Subjects
Ligand, Organic Chemistry, chemistry.chemical_element, Crystal structure, Borane, Medicinal chemistry, Methane, Rhodium, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Organic chemistry, Chelation, Physical and Theoretical Chemistry, Dichloromethane
Abstract

The first dibenzophospholyl(diphenylphosphino)methane−borane hybrid ligand has been prepared from a Pd-catalyzed reaction of (chloromethyl)diphenylphosphine−borane with the dibenzophospholyl anion. This borane precursor is readily synthesized using a promising new reaction of diphenylphosphine−borane with dichloromethane, under phase transfer catalysis (PTC) conditions. The dibenzophospholyl(diphenylphosphino)methane−borane acts as a chelating P−(η2-BH3) ligand to afford an air-stable Rh(I) complex. The X-ray crystal structure of this complex shows complexation of both benzophospholyl and borane moieties.

Published
2009

33. Highly regioselective palladium-catalyzed methoxycarbonylation of styrene using chiral ferrocene- and biphosphole-based ligands

Author

Philippe Kalck, Lisa Diab, Maryse Gouygou, Eric Manoury, and Martine Urrutigoïty

Subjects
chemistry.chemical_compound, chemistry, Ferrocene, Organic Chemistry, Drug Discovery, Organic chemistry, chemistry.chemical_element, Regioselectivity, Biochemistry, Palladium, Catalysis, Styrene
Abstract

The methoxycarbonylation of styrene has been studied using Pd(OAc)2/L/acid catalytic systems with L being chiral ferrocene- and biphosphole-based ligands. Good activities are obtained in mild conditions. Chemoselectivities and regioselectivities (up to 98% in favour of the branched isomer) are excellent but enantioselectivities remain moderate (ee up to 17%).

Published
2008

34. Rh- and Pt-catalyzed cycloisomerization of enynes derived from terpenes

Author

Odile Dechy-Cabaret, Martine Urrutigoïty, Philippe Kalck, Philippe Costes, and Jochen Weckesser

Subjects
Enyne, Diene, Chemistry, Stereochemistry, chemistry.chemical_element, Homogeneous catalysis, General Chemistry, Ring (chemistry), Cyclopropane, Rhodium, Inorganic Chemistry, chemistry.chemical_compound, Cycloisomerization, Moiety
Abstract

The Rh-catalyzed cycloisomerization of new terpenoid derivatives featuring an O-tethered enyne unexpectedly leads to polycyclic derivatives containing an inner cyclopropane ring or a diene moiety, depending on the structure of the enyne, as observed in the PtCl2-catalyzed processes. Copyright © 2008 John Wiley & Sons, Ltd.

Published
2008

35. Critical solvent effect on the chiral recognition of a catalytic species by a chiral substrate

Author

Eric Manoury, Lisa Diab, Maryse Gouygou, Philippe Kalck, and Martine Urrutigoïty

Subjects
Process Chemistry and Technology, Substrate (chemistry), chemistry.chemical_element, Toluene, Medicinal chemistry, Catalysis, Reaction rate, chemistry.chemical_compound, chemistry, Ferrocene, Organic chemistry, Physical and Theoretical Chemistry, Solvent effects, Acetonitrile, Palladium
Abstract

In the diastereoselective cyclocarbonylation of isopulegol and isolimonene catalysed by the non-chiral [PdCl 2 L 2 ] palladium complexes (L = PPh 3 , L 2 = bis(diphenylphosphino)-butane or -ferrocene), the diastereoisomeric excess is enhanced by a factor of 1.5–2 when toluene is substituted by chloro-solvents. A less significant effect is noted when using more coordinating solvents such as acetonitrile and THF. In chloro-solvents reaction rates are faster than in toluene, isopropanol, acetonitrile or THF.

Published
2007

36. Modifications of the chemical structure of terpenes in antiplasmodial and antifungal drug research

Author

Françoise Benoit-Vical, Odile Dechy-Cabaret, Antoine Berry, Martine Urrutigoïty, David Olagnier, Marie-Denise Linas, and Philippe Costes

Subjects
Cyclopentenone, Antifungal Agents, Stereochemistry, Chemistry, Pharmaceutical, Chemical structure, Monoterpene, Plasmodium falciparum, Clinical Biochemistry, Antifungal drug, Pharmaceutical Science, Microbial Sensitivity Tests, Biochemistry, Terpene, Antimalarials, Inhibitory Concentration 50, Structure-Activity Relationship, chemistry.chemical_compound, Parasitic Sensitivity Tests, Candida albicans, parasitic diseases, Drug Discovery, Animals, Structure–activity relationship, Organic chemistry, Molecular Biology, Molecular Structure, Chemistry, Organic Chemistry, Biological activity, Terpenoid, Monoterpenes, Molecular Medicine
Abstract

Pure natural monoterpenes were evaluated in vitro for their antiplasmodial activities against Plasmodium falciparum. Chemically modified terpenes were also tested to see whether the introduction of an alkyne, a cyclopropane, a diene, or a cyclopentenone moiety had an influence on the biological activity. The IC(50) obtained on a chloroquine-resistant strain of Plasmodium (FcM29-Cameroon) showed moderate activity, but with the alkyne and the cyclopentenone derivatives showing a promising enhancement of activity compared with the parent molecules. On the contrary, no antifungal activity was found in vitro using Candida albicans. Given the observed antiplasmodial activity of some of these modified monoterpenes, new monoterpene derivatives could be the basis for new antimalarial drugs to be researched.

Published
2007

37. Recent improvements in the alkoxycarbonylation reaction catalyzed by transition metal complexes

Author

Martine Urrutigoïty, Philippe Kalck, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Coordination sphere, Denticity, Hydroesterification, Palladium(II), chemistry.chemical_element, Alcohol, Catalysis, CO chemistry, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Transition metal, Microwave irradiation, Ionic liquid, Materials Chemistry, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Esters synthesis, Palladium, Alkoxycarbonylation
Abstract

International audience; Palladium plays an almost exclusive role as catalyst in the alkoxycarbonylation of various substrates to produce esters or lactones, by incorporation of CO and a alcohol. The coordination sphere can be adapted by introduction of mono- or bidentate phosphorus-containing ligands, providing efficient tools to obtain with high turnovers, regio- and even enantioselectivities the incorporation of a COOR function onto a carbon atom. The use of CO, surrogates such as formates or even carbon dioxide are explored to operate this reaction. Adapted catalytic systems have been designed, sometimes with the assistance of microwave irradiation, to have an immobilization in Ionic Liquids, or scCO2, or on various supports. Even if less expensive metals than palladium are explored to provide comparable performances, green efficient tools are at the disposal of chemists leading to bulk and fine products as well.

Published
2015

38. Selectivity controlled by ligand tuning in the palladium-catalysed cyclocarbonylation: Synthesis of new γ and δ lactones from a natural sesquiterpene

Author

Jean Claude Daran, Jamal El Karroumi, Eric Manoury, Maryse Gouygou, Martine Urrutigoïty, Ahmed Benharref, Abderrahim El Haib, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Xantphos, Ligand, Process Chemistry and Technology, chemistry.chemical_element, Homogeneous catalysis, Bite angle, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Diphosphines, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Selectivity, Phosphine, Palladium
Abstract

International audience; The cyclocarbonylation of homoallylic alcohols, derived from α-atlantone, catalysed by [Pd(Cl2)L2]/SnCl2] system, afforded new γ and δ lactones as the main products with high selectivities. The regiochemical control depends on the nature of phosphines involved. Catalysts based on monophosphines with large cone angles such as tricyclohexyl phosphine produce the six-membered ring lactones with selectivities up to 80%, while diphosphines with wide bite angle such as xantphos are found to favor the five-membered ring lactones with up to 99% selectivity. Monocrystals of the γ and δ lactones suitable for X-ray diffraction analysis have been obtained and the stereochemistry of the lactones 5a,a′ and 6 have been elucidated. This study is the first example of an attractive catalytic transformation of one single natural sesquiterpene easily available from bio-renewable resources to obtain either γ- or δ-lactones.

Published
2015

39. Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives

Author

Philippe Kalck, Jean-Cyrille Hierso, Philippe Meunier, Aziz Fihri, Martine Urrutigoïty, Duc Hanh Nguyen, Laboratoire de Catalyse et Chimie Fine, Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques, Laboratoire de Synthèse et Electrosynthèse Organométalliques (LSEO), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), and Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS )

Subjects
Allylic rearrangement, Monoterpene, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, Inorganic Chemistry, [ CHIM.CATA ] Chemical Sciences/Catalysis, chemistry.chemical_compound, Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, palladium catalysis, ComputingMilieux_MISCELLANEOUS, Amination, 010405 organic chemistry, Chemistry, [ CHIM.COOR ] Chemical Sciences/Coordination chemistry, monoterpenes, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 0104 chemical sciences, ferrocenylphosphine, Ferrocene, allylic amination, Selectivity, Metallocene, Palladium
Abstract

Ferrocenylphosphines added to [Pd(µ-Cl)(η3-C3H5)]2 dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1′-bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial interest. Copyright © 2006 John Wiley & Sons, Ltd.

Published
2006

40. Hydride Route for the Palladium‐Catalysed Cyclocarbonylation of Monoterpenes

Author

Philippe Kalck, Martine Urrutigoïty, Gábor Laurenczy, and Duc Hanh Nguyen

Subjects
Inorganic Chemistry, chemistry, Catalytic cycle, Hydride, Monoterpene, Cationic polymerization, chemistry.chemical_element, Organic chemistry, Reactivity (chemistry), Nuclear magnetic resonance spectroscopy, Carbonylation, Medicinal chemistry, Palladium
Abstract

This paper focuses on the mechanism by which a monoterpene undergoes a cyclocarbonylation reaction catalysed by a palladium complex. Evidence is provided, based on intermediate species observed under pressure or with various ligands, that the catalytic cycle follows a hydride route starting from [Pd(H)(SnCl3)L-2], The [Pd(H)(SnCl3)L-2] complexes (L = PPh3 or PCy3) have been observed for the first time by multinuclear NMR spectroscopy. Cationic hydride complexes or palladium(0) precursors show either no or poor reactivity. Studies related to model platinum complex chemistry have detected an acylplatinum species. Most of the observations have been done on the cyclocarbonylation of isopulegol, di-hydromyrcenol or isolimonene into the corresponding lactones or cyclopentanones. The use of dihydromyrcene allowed us to observe the acylplatinum complex and the corresponding elusive acylpalladium species. The co-catalytic role of SnCl2 is also demonstrated.

Published
2005

41. Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates

Author

Aziz Fihri, Régine Amardeil, Anthony Vion, Philippe Kalck, Philippe Meunier, Jean-Cyrille Hierso, Duc Hanh Nguyen, and Martine Urrutigoïty

Subjects
chemistry.chemical_compound, Allylic rearrangement, chemistry, Nucleophile, Allyl acetate, Morpholine, Diphosphines, Organic chemistry, chemistry.chemical_element, General Chemistry, Amination, Palladium, Catalysis
Abstract

Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of economical (resource- and energy-saving) and sustainable chemistry (high selectivity, no additive, low metal content, and thus easier purification).

Published
2005

42. [Pd(H)(SnCl3)L2]: The key active species in the catalyzed alkoxycarbonylation reaction of terminal alkenes

Author

Duc Hanh Nguyen, Martine Urrutigoïty, Philippe Kalck, and Yannick Coppel

Subjects
Chemistry, Hydride, Ligand, Organic Chemistry, Biochemistry, Medicinal chemistry, Catalysis, Inorganic Chemistry, Metal, visual_art, Materials Chemistry, visual_art.visual_art_medium, Organic chemistry, Physical and Theoretical Chemistry, Carbonylation
Abstract

The four complexes [Pd(H)(Cl)L 2 ] and [Pd(H)(SnCl 3 )L 2 ], L = PPh 3 , PCy 3 , have been synthesized and fully characterized by multinuclear NMR. They represent the active species of the hydride palladium-catalyzed alkoxycarbonylation of terminal alkenes. Isolation of the model acylplatinum complex, resulting from the carbonylation of dihydromyrcene, clearly shows that SnCl 2 as co-catalyst produces a SnCl 3 ligand which modulates the metal center electron density.

Published
2005

43. An efficient catalytic system for cyclocarbonylation of terpenes into lactones

Author

Frédéric Hebrard, Philippe Kalck, Alfonso Polo, Josep Duran, Martine Urrutigoïty, and Duc Hanh Nguyen

Subjects
chemistry.chemical_classification, Ligand, Chemistry, Alcohol, Butane, General Chemistry, Catalysis, Inorganic Chemistry, Terpene, chemistry.chemical_compound, Organic chemistry, Chelation, Lactone, Geraniol
Abstract

Three different kinds of representative monoterpenic alcohol are involved in the palladium-catalysed cyclocarbonylation reaction. Lactone formation is shown to occur when cyclic (1), tertiary (3) and primary allylic alcohol (7) functions are reacted, in the presence of CO with [HPd(SnCl3)L2] as the active catalytic species. Good yields and selectivities can easily be reached for isopulegol (1), and dihydromyrcenol (3). However, more modest results are obtained for the functionalization of geraniol into the original lactone (9). This lactone can be largely favoured by using a basic chelating diphosphine ligand such as 1,4-bis(diphenylphosphino)butane. Copyright © 2005 John Wiley & Sons, Ltd.

Published
2005

44. Asymmetric catalysis induced by the substrate itself

Author

Martine Urrutigoïty and Philippe Kalck

Subjects
Denticity, Coordination sphere, Chemistry, Enantioselective synthesis, Substrate (chemistry), Photochemistry, Combinatorial chemistry, Asymmetric induction, Catalysis, Inorganic Chemistry, Asymmetric carbon, Materials Chemistry, Physical and Theoretical Chemistry, Chirality (chemistry)
Abstract

This review presents the main potentialities provided by a substrate bearing at least one chiral carbon atom which is the source of stereodifferentiation when a catalytic functionalization is performed. This chirality control introduced by the substrate itself is an alternative to the classical strategy of introducing chiral ligands in the coordination sphere of a metal, although the level of diastereoselectivity is lower in the former system. We describe how the substrate can induce asymmetry; several catalytic mechanisms are detailed. This relatively unexplored concept could have potential as abundant bidentate non-chiral ligands can be used to tune the stereocontrol of the substrate functionalization.

Published
2004

45. Tandem Palladium‐Catalyzed Cyclocarbonylation of Isolimonene: A Mechanistic Investigation and Theoretical Calculations on the Fully Diastereoselective Step

Author

Philippe Kalck, Géraldine Lenoble, Martine Urrutigoïty, Corinne Lacaze-Dufaure, and Claude Mijoule

Subjects
Inorganic Chemistry, Bond length, Steric effects, Elimination reaction, Trigonal bipyramidal molecular geometry, Crystallography, Chemistry, Stereochemistry, Asymmetric carbon, Bond order, Asymmetric induction, Stereocenter
Abstract

Cyclocarbonylation of isolimonene catalyzed by complexes of the type [HPd(SnCl3)L2] provides two cyclopentanone isomers (2a and 2b) containing two new stereogenic centers with a good diastereomeric excess (up to 69 % with L2 = dppf). These results show that chiral phosphane ligands are not necessary to ensure asymmetric induction. The diastereomeric excess is due, in fact, to the substrate itself, assisted by the steric hindrance of the diphosphanes. A full characterization of the two isomers by 1H, 13C and DPFGSE NOE NMR spectroscopy gives all the signal assignations and all the positions of the substituents of interest on the chiral carbon atoms. In order to have a better understanding of the catalytic process, we also present a density functional study of the crucial intermediate species 4 involved in the proposed catalytic cycle. Our calculations show that there is no coordination of the C=C bond in an exo mode. Conversely, we have found a pentacoordinate species with a trigonal bipyramidal geometry in which the C=C bond is coordinated in an endo mode. Selected bond lengths and bond orders are reported. The calculated net charge distribution supports the cyclization process, which proceeds through a C−C(O) and a C−Pd coupling. A β-hydride elimination reaction of 4 provides the two 2a and 2b isomers. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Published
2004

46. Dihydromyrcenol carbonylation catalyzed by palladium–tin precursors: selectivity of the reaction drawn by the experimental conditions and the co-reactants

Author

Géraldine Lenoble, Philippe Kalck, and Martine Urrutigoïty

Subjects
chemistry.chemical_classification, Double bond, Organic Chemistry, chemistry.chemical_element, Biochemistry, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Materials Chemistry, Organic chemistry, Methanol, Physical and Theoretical Chemistry, Tin, Selectivity, Carbonylation, Isomerization, Palladium
Abstract

The methoxycarbonylation of dihydromyrcenol 1 has been carried out in the presence of the catalytic system [PdCl2(PPh3)2]–SnCl2·2H2O–2PPh3. This study shows that it is possible to reduce the amounts of isomerization of the terminal double bond and the dehydration side-reaction of the tertiary alcoholic function. According to the experimental conditions (PCO=40 or 100 bar, concentration of methanol, experiment duration, temperature) it is possible to orient the reaction towards the three ‘linear’ esters 4, 5, 6, and lactone 8. This latter product has been exclusively obtained when the acidity of the medium is controlled. Nevertheless it is more difficult to obtain one ester from each others.

Published
2002

47. ChemInform Abstract: Novel C1-Symmetric Dibenzophosphole Ligands: Application in Hydroformylation Reactions

Author

Maryse Gouygou, Martine Urrutigoïty, Duc Hanh Nguyen, Françoise Colobert, Frédéric R. Leroux, Laurence Bonnafoux, Abdelhouad Oukhrib, Sandrine Waifang, and Armen Panossian

Subjects
Chemistry, Organic chemistry, General Medicine, Hydroformylation
Abstract

A series of dibenzophosphole ligands are screened for Rh-catalyzed hydroformylation reactions of styrenes and 1-octene.

Published
2014

48. Novel C1-symmetric dibenzophosphole ligands: application in hydroformylation reactions

Author

Maryse Gouygou, Armen Panossian, Sandrine Waifang, Françoise Colobert, Duc Hanh Nguyen, Abdelhouad Oukhrib, Martine Urrutigoïty, Frédéric R. Leroux, Laurence Bonnafoux, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie des substances naturelles, Université Cadi Ayyad [Marrakech] (UCA), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Steric effects, 010405 organic chemistry, Chemistry, Organic Chemistry, Phosphole, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Rhodium, Catalysis, chemistry.chemical_compound, Drug Discovery, Electronic effect, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Hydroformylation
Abstract

International audience; A new family of non-symmetrical disubstituted dibenzophospholes possessing different steric and electronic effects have been synthesized and characterized. Their preliminary evaluation in rhodium-catalyzed hydroformylation reactions is presented.

Published
2014

49. Hydroaminomethylation of Styrene Catalyzed by Rhodium Complexes Containing Chiral Diphosphine Ligands and Mechanistic Studies: Why Is There a Lack of Asymmetric Induction?

Author

Delphine Crozet, Christos E. Kefalidis, Laurent Maron, Martine Urrutigoïty, Philippe Kalck, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), 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), 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), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], Coordination sphere, Chemistry, Stereochemistry, Ligand, Regioselectivity, General Chemistry, Asymmetric induction, Catalysis, Reductive elimination, 3. Good health, Enamine, chemistry.chemical_compound, Cascade reaction, [CHIM]Chemical Sciences, Piperidine
Abstract

International audience; Various chiral diphosphine ligands (P–P) have been introduced in the coordination sphere of neutral or cationic rhodium complexes, and the generated species catalyze efficiently the hydroaminomethylation reaction of styrene with piperidine. The diphospholane ligand family is particularly adapted to this tandem reaction leading to the branched amine with good chemo- and regioselectivity. We analyzed in detail the main reasons why the reaction proceeds with no enantioselectivity. Catalytic and HP-NMR experiments reveal the presence of the [Rh(H)(CO)2(P–P)] species as the resting state. DFT calculations allow us to elucidate the mechanism of the hydrogenation of the branched (Z) or (E)-enamine. From the [Rh(H)(CO)(P–P)] active species, the coordination of the two enamine isomers, the hydride transfer, the H2 activation, and then the final reductive elimination follow similar energetic pathways, explaining the lack of enantioselectivity for the present substrates. Analysis of the energy-demanding steps highlights the formation of the active species as crucial for this rate-limiting hydrogenation reaction.

Published
2014

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