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32 results on '"Bastien Chatelet"'

1. Energy‐Efficient Iodine Uptake by a Molecular Host⋅Guest Crystal

Author

Xue Yang, Chunyang Li, Michel Giorgi, Didier Siri, Xavier Bugaut, Bastien Chatelet, Didier Gigmes, Mehdi Yemloul, Virginie Hornebecq, Anthony Kermagoret, Sophie Brasselet, Alexandre Martinez, David Bardelang, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU), Université de Strasbourg (UNISTRA), Matériaux divisés, interfaces, réactivité, électrochimie (MADIREL), Centre National de la Recherche Scientifique (CNRS), MOSAIC (MOSAIC), Institut FRESNEL (FRESNEL), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Fédération des Sciences Chimiques de Marseille (FRSCM), Laboratoire d'innovation moléculaire et applications (LIMA), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[SPI.OPTI]Engineering Sciences [physics]/Optics / Photonic, [CHIM]Chemical Sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, General Medicine, Catalysis
Abstract

International audience; Recently, porous organic crystals (POC) based on macrocycles have shown exceptional sorption and separation properties. Yet, the impact of guest presence inside a macrocycle prior to adsorption has not been studied. Here we show that the inclusion of trimethoxybenzyl-azaphosphatrane in the macrocycle cucurbit-[8]uril (CB[8]) affords molecular porous host-guest crystals (PHGC-1) with radically new properties. Unactivated hydrated PHGC-1 adsorbed iodine spontaneously and selectively at room temperature and atmospheric pressure. The absence of (i) heat for material synthesis, (ii) moisture sensitivity, and (iii) energy-intensive steps for pore activation are attractive attributes for decreasing the energy costs. 1 H NMR and DOSY were instrumental for monitoring the H 2 O/I 2 exchange. PHGC-1 crystals are non-centrosymmetric and I 2-doped crystals showed markedly different second harmonic generation (SHG), which suggests that iodine doping could be used to modulate the non-linear optical properties of porous organic crystals.

Published
2022
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2. Sequential Formation of Heteroternary Cucurbit[10]uril (CB[10]) Complexes

Author

Chunyang Li, Anne‐Doriane Manick, Yuxi Zhao, Fengbo Liu, Bastien Chatelet, Roselyne Rosas, Didier Siri, Didier Gigmes, Valerie Monnier, Laurence Charles, Julie Broggi, Simin Liu, Alexandre Martinez, Anthony Kermagoret, David Bardelang, Aix-Marseille Université/CNRS, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The State Key Laboratory of Refractories and Metallurgy, School of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, People’s Republic of China, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), and Fédération Sciences Chimiques Marseille (FSCM)

Subjects
Organic Chemistry, [CHIM]Chemical Sciences, General Chemistry, Catalysis
Abstract

International audience; The globular and monocationic guest molecule trimethyl-azaphosphatrane (AZAP, a protonated Verkade superbase) was shown to form a host:guest 1 : 1 complex with the cucurbit[10]uril (CB[10]) macrocycle in water. Molecular dynamics calculations showed that CB[10] adopts an 8-shape with AZAP occupying the majority of the internal space, CB[10] contracting around AZAP and leaving a significant part of the cavity unoccupied. This residual space was used to co-include planar and monocationic co-guest (CG) molecules, affording heteroternary CB[10]•AZAP•CG complexes potentially opening new perspectives in supramolecular chemistry.

Published
2022
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3. The Chloroazaphosphatrane Motif for Halogen Bonding in Solution

Author

Damien Hérault, Jean-Pierre Dutasta, Bohdan Biletskyi, Xavier Bugaut, Sabine Michaud-Chevalier, Alexandre Martinez, Bastien Chatelet, Anne-Doriane Manick, Jian Yang, Chunyang Li, David Givaudan, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, Denticity, Halogen bond, Chemistry, Superbase, Oxide, Protonation, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Nmr titration, Halogen, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract

International audience; Chloroazaphosphatranes, the corresponding halogenophosphonium cations of the Verkade superbases, were evaluated as a new motif for halogen bonding (XB). Their modulable synthesis allowed for synthetizing chloroazaphosphatranes with various substituents on the nitrogen atoms. The binding constants determined from NMR titration experiments for Cl − , Br − , I − , AcO − , and CN − anions are comparable to those obtained with conventional iodine-based monodentate XB receptors. Remarkably, the protonated azaphosphatrane counterparts display no affinity for anions under the same conditions. The strength of the XB interaction is, to some extent, related to the basicity of the corresponding Verkade superbase. The halogen bonding abilities of this new class of halogen donor motif were also revealed by the Δδ(31 P) NMR shift observed in CD 2 Cl 2 solution in the presence of triethylphosphine oxide (TEPO). Thus, chloroazaphosphatranes constitute a new class of halogen bond donors, expanding the repertory of XB motifs mainly based on C Ar −I bonds.

Published
2021
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4. Synthesis, Characterizations and Applications of Fluoroazaphosphatranes

Author

Anne‐Doriane Manick, Jean‐Pierre Dutasta, Paola Nava, Véronique Dufaud, Guohua Gao, Bastien Chatelet, Alexandre Martinez, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University [Shangaï] (ECNU), Vrije Universiteit Amsterdam [Amsterdam] (VU), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2)

Subjects
Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Carbonates, Epoxy Compounds, General Chemistry, Carbon Dioxide, Biochemistry, Catalysis
Abstract

International audience; Haloazaphosphatranes are the halogenated parents of proazaphosphatranes, also known as Verkade's superbase. While the synthesis of iodo-, bromo-and chloroazaphosphatranes was reported more than thirty years ago by J. G. Verkade, the first synthesis of fluoroazaphosphatranes was only described in 2018 by Stephan et al. Currently, no common and versatile procedure exists to access fluoroazaphosphatranes platform with different structural characteristics. In this report, a new and simple synthesis of this class of compounds was developed based on the nucleophilic attack of the fluoride anion on chloroazaphosphatrane derivatives with good to high isolated yields for the corresponding fluoroazaphosphatranes (70-92%). The scope of the reaction was widened to fluoroazaphosphatranes bearing various substituents and X-ray molecular structures of two of them are reported. The stability of fluoroazaphosphatranes toward nucleophilic solvents like water has been investigated. As they revealed much more robust cations than their chloroazaphosphatrane parents, their chloride salts were tested as organocatalysts for the formation of cyclic carbonates from epoxides and CO 2. Fluoroazaphosphatranes proved to be both efficient and stable catalytic systems for CO 2 conversion with catalytic activities similar to those of azaphosphatranes, and no decomposition of the cation was observed at the end of reaction.

Published
2022
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5. Access to the Syn diastereomers of cryptophane cages using HFIP

Author

Oriane Della-Negra, Yoann Cirillo, Thierry Brotin, Jean-Pierre Dutasta, Pierre-Loic Saaidi, Bastien Chatelet, Alexandre Martinez, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Génomique métabolique (UMR 8030), Genoscope - Centre national de séquençage [Evry] (GENOSCOPE), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

The use of the HFIP/bisulfate salt combination provides convenient and fast access to syn-cryptophanes.

Published
2022
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6. Access to the

Author

Oriane, Della-Negra, Yoann, Cirillo, Thierry, Brotin, Jean-Pierre, Dutasta, Pierre-Loic, Saaidi, Bastien, Chatelet, and Alexandre, Martinez

Abstract

Cryptophane cages can adopt either an

Published
2022

7. Hemicryptophane Cages with a

Author

Chunyang, Li, Anne-Doriane, Manick, Marion, Jean, Muriel, Albalat, Nicolas, Vanthuyne, Jean-Pierre, Dutasta, Xavier, Bugaut, Bastien, Chatelet, and Alexandre, Martinez

Abstract

Two new hemicryptophanes combining a cyclotriveratrylene unit with either an aminotrisamide or a tris(2-aminoethyl)amine (tren) moiety have been synthesized. Although a conventional synthesis approach was used, the molecular cages obtained are devoid of the expected

Published
2021

8. Azaphosphatranes Catalyzed Strecker Reaction in the Presence of Water

Author

Chunyang Li, Jian Yang, Anne-Doriane Manick, Alexandre Martinez, Véronique Dufaud, Bastien Chatelet, Xavier Bugaut, Damien Hérault, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Cyanide, Strecker amino acid synthesis, education, General Chemistry, Cyanation, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Organocatalysis, Organic chemistry, [CHIM]Chemical Sciences, Trimethylsilyl cyanide
Abstract

International audience; Azaphosphatranes were found to act as efficient organocatalysts in the presence of water for the cyanation of differently substituted imines. A relatively safer source of cyanide, trimethylsilyl cyanide (TMSCN), was used, and excellent yields could be obtained with only 0.05 mol % of catalyst. The influence of acidity of azaphosphatranes on catalytic activity as well as the role of azaphosphatranes in the mechanism of the reaction were also investigated.

Published
2020
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9. Highly Selective Fluoride Recognition by a Small Tris-Urea Covalent Cage

Author

Cédric Colomban, Sabine Chevallier-Michaud, Jean-Pierre Dutasta, Alexandre Martinez, Bastien Chatelet, Magalie Delecluse, Delphine Moraleda, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Tris, 010405 organic chemistry, Organic Chemistry, macromolecular substances, 010402 general chemistry, Highly selective, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Covalent bond, Polymer chemistry, Urea, Moiety, [CHIM]Chemical Sciences, Cage, Fluoride
Abstract

International audience; A highly selective recognition of fluoride was achieved through the design of a small hemicryptophane cage (3) presenting a southern tris-urea hosting moiety. The resulting host−guest complex has been characterized by electrospray ionization-highresolution mass spectrometry, 1 H and 19 F NMR, and X-ray diffraction techniques. In particular, X-ray diffraction analysis of [3•F − ] reveals that the encapsulation of one fluoride, within 3, occurs through NH•••F − H-bonding with the six NH residues of the tris-urea ligand. An association constant of 1200 M −1 was extracted from 1 H NMR titration experiments, indicating that efficient fluoride binding also occurs in solution. Finally, in sharp contrast with previously reported urea-based hemicryptophane hosts, the small preorganized cavity found in 3 allows for an exclusive selectivity for fluoride over other competing halides.

Published
2020
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10. Verkade's Superbase as an Organocatalyst for the Strecker Reaction

Author

Alexandre Martinez, Véronique Dufaud, Bastien Chatelet, Damien Hérault, Jian Yang, and Fabio Ziarelli

Subjects
Reaction mechanism, 010405 organic chemistry, Organic Chemistry, Superbase, Strecker amino acid synthesis, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Nitrogen, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Organocatalysis, Physical and Theoretical Chemistry, Trimethylsilyl cyanide, Selectivity
Abstract

Proazaphosphatranes-Verkade's superbases-proved to be efficient organocatalysts for the Strecker reaction between protected imines and trimethylsilyl cyanide (TMSCN). Excellent to quantitative yields were reached and, compared to other systems, only low catalyst loading and short reaction times were required for the reaction to proceed efficiently. A remarkable initial turnover frequency (TOF), close to 105 h–1, was achieved, associated with an excellent selectivity since no side reactions were observed. A reaction mechanism was proposed and the key role played by the apical nitrogen in the proazaphosphatrane structure was demonstrated.

Published
2018
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11. Synthesis of Gold(I) Complexes Bearing Verkade's Superbases

Author

Bastien Chatelet, Hervé Clavier, Paola Nava, Alexandre Martinez, Institut des Sciences Moléculaires de Marseille (ISM2), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Lability, ved/biology, Ligand, Superbase, ved/biology.organism_classification_rank.species, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, chemistry.chemical_compound, Transmetalation, chemistry, Phosphorus atom, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene, Conjugate acid
Abstract

International audience; Proazaphosphatranes, also known as Verkade's superbases, have been investigated as ligands for gold(I). If the coordination to the gold center by the phosphorus atom suggests phosphine‐like behavior, gold(I)‐containing Verkade's superbase complexes could also be prepared from the weak conjugate acid azaphosphatrane by the formation of the corresponding silver complex and subsequent transmetalation to gold, similarly to the synthetic route used for complexes bearing N‐heterocyclic carbene ligands (NHCs). A competitive transmetalation experiment highlighted the higher lability of Verkade's superbases compared with NHCs. Furthermore, combined theoretical and experimental studies showed that they display strong σ‐donor ability, better than phosphines and similar to NHCs. Thus, some specific properties of both NHCs and phosphines are combined in Verkade's superbases, thereby providing a new approach to tuning the ligand properties of gold(I) complexes.

Published
2017
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12. Enantio- and Substrate-Selective Recognition of Chiral Neurotransmitters with

Author

Jian, Yang, Bastien, Chatelet, Véronique, Dufaud, Damien, Hérault, Marion, Jean, Nicolas, Vanthuyne, Jean-Christophe, Mulatier, Delphine, Pitrat, Laure, Guy, Jean-Pierre, Dutasta, and Alexandre, Martinez

Subjects
Neurotransmitter Agents, Molecular Structure, Ammonium Compounds, Stereoisomerism
Abstract

We report on the synthesis of

Published
2020

13. Enantio- and Substrate-Selective Recognition of Chiral Neurotransmitters with C 3 -Symmetric Switchable Receptors

Author

Damien Hérault, Marion Jean, Laure Guy, Delphine Pitrat, Nicolas Vanthuyne, Jean-Christophe Mulatier, Bastien Chatelet, Alexandre Martinez, Véronique Dufaud, Jean-Pierre Dutasta, Jian Yang, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Enantioselective synthesis, Substrate (chemistry), Protonation, Stereoisomerism, 010402 general chemistry, 01 natural sciences, Biochemistry, 3. Good health, 0104 chemical sciences, Deprotonation, Enantiopure drug, Molecule, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Selectivity
Abstract

International audience; We report on the synthesis of C 3-symmetric enantiopure cage molecules 1, which exhibit remarkable to exclusive enantioselective recognition properties toward chiral ammonium neurotransmitters. Strong changes in the substrate selectivity are also observed when different stereoisomers of 1 are used. Furthermore, protonation/deprotonation induces a reversible modification of the conformation of 1, which switches from an imploded to an inflated form, leading to ejection and reuptake of the guest initially encaged inside the cavity.

Published
2020
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14. Enantiopure encaged Verkade's superbases: Synthesis, chiroptical properties, and use as chiral derivatizing agent

Author

Damien Hérault, Stéphane Grass, Bastien Chatelet, Alexandre Martinez, Nicolas Vanthuyne, Véronique Dufaud, Jean-Pierre Dutasta, Marion Jean, Jérôme Lacour, Muriel Albalat, Jian Yang, Vincent Robert, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de chimie physique [Genève], Université de Genève (UNIGE), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Genève = University of Geneva (UNIGE), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Circular dichroism, Stereochemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Analytical Chemistry, Drug Discovery, [CHIM]Chemical Sciences, ECD, Enantiomeric excess, Spectroscopy, Chiral derivatizing agent, enantiopure cages, Pharmacology, Verkade's superbase, 010405 organic chemistry, Chemistry, Organic Chemistry, Absolute configuration, Phosphazide, 0104 chemical sciences, Enantiopure drug, chiral derivatizing agent, ddc:540, Chirality (chemistry)
Abstract

International audience; Verkade's superbases, entrapped in the cavity of enantiopure hemicryptophane cages, have been synthesized with enantiomeric excess (ee) superior to 98%. Their absolute configuration has been determined by using electronic circular dichroism (ECD) spectroscopy. These enantiopure encaged superbases turned out to be efficient chiral derivatizing agents for chiral azides, underlining that the chirality of the cycloveratrylene (CTV) macrocycle induces different magnetic and chemical environments around the phosphazide functions.

Published
2020
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15. Positive Cooperative Effect in Ion‐Pair Recognition by a Tris‐urea Hemicryptophane Cage

Author

Innocenzo de Riggi, Françoise Duprat, Magalie Delecluse, Vincent Robert, Bastien Chatelet, Delphine Moraleda, Sabine Michaud-Chevallier, Cédric Colomban, Jean-Pierre Dutasta, Alexandre Martinez, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire de chimie quantique et de modélisation moléculaire (LCQMM), Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tris, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Organic Chemistry, Salt (chemistry), Cooperativity, General Chemistry, Ion pairs, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Urea, Moiety, [CHIM]Chemical Sciences, Host–guest chemistry, Cage, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The synthesis of a hemicryptophane cage combining a CTV unit with a C 3 symmetrical moiety bearing three urea functions is reported. This host was found to bind anions with higher binding constants than other previously reported hemicryptophanes. Due to its heteroditopic character this cage proved to be an efficient ion-pair receptor. The best cooperativity effect was observed for the tetramethy-lammonium bromide (TMABr) salt, which was confirmed and rationalized by DFT calculations.

Published
2019
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16. Endohedral Functionalized Cage as a Tool to Create Frustrated Lewis Pairs

Author

Alexandre Martinez, Véronique Dufaud, Jian Yang, Damien Hérault, Sabine Michaud-Chevallier, Vincent Robert, Bastien Chatelet, Jean-Pierre Dutasta, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Nanjing University of Science and Technology [Nanjing], École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU)

Subjects
010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Superbase, Supramolecular chemistry, chemistry.chemical_element, Substrate (chemistry), Homogeneous catalysis, General Medicine, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Frustrated Lewis pair, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Lewis acids and bases, ComputingMilieux_MISCELLANEOUS, Titanium
Abstract

International audience; A frustrated Lewis pair (FLP) system was obtained by confinement of the Lewis base partner, a Verkades super-base, in a molecular cavity. Whereas the model superbase lacking cavity displayed no catalytic activity in Morita-Baylis-Hillman (MBH) reactions, when associated to titanium (IV) chloride, the encaged superbase turns out to be an efficient catalyst under the same conditions. The crucial role of the endohedral functionalized cage on catalytic performance was further demonstrated by the fact that model superbases with bulky substituents were much less efficient to produce active catalysts, as well as by inhibition and substrate selection experiments. 31 P NMR spectroscopy and mass spectrometry experiments evidenced that no interaction between the Lewis acidic and basic partners occurred when the superbase was capped by a cycloveratrylene (CTV) unit, thus creating a true FLP active system.

Published
2018
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17. Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host-Guest Systems

Author

Dawei Zhang, Vincent Robert, Jean-Pierre Dutasta, Eloisa Serrano, Bastien Chatelet, Olivier Perraud, Alexandre Martinez, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, East China Normal University [Shangaï] (ECNU), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Quantique, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Chemistry, Intermolecular force, Supramolecular chemistry, food and beverages, Cooperativity, Nanotechnology, Aromaticity, 010402 general chemistry, 01 natural sciences, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Chemical physics, [CHIM]Chemical Sciences, Molecule, Physical and Theoretical Chemistry
Abstract

International audience; The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation-pi and anion-pi interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron-poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion-pair recognition. Wavefunction calculations highlight how short-and long-range interactions interfere in this recognition process, suggesting that a disruption of anion-p interactions can occur in the presence of a co-bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.

Published
2015
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18. Chiral Discrimination of Ammonium Neurotransmitters by C3 -Symmetric Enantiopure Hemicryptophane Hosts

Author

Alexandre Martinez, Aline Schmitt, Solène Collin, Bastien Chatelet, and Jean-Pierre Dutasta

Subjects
Pharmacology, Titration curve, 010405 organic chemistry, Stereochemistry, Chemistry, Organic Chemistry, Diastereomer, Supramolecular chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health, Analytical Chemistry, chemistry.chemical_compound, Enantiopure drug, Drug Discovery, Molecule, Ammonium, Enantiomer, Chirality (chemistry), Spectroscopy
Abstract

Enantiopure hemicryptophanes efficiently discriminate chiral ammonium neurotransmitters. The ephedrine and norephedrine molecules associate with hemicryptophane hosts to form 1:1 and 1:2 host-guest complexes. Binding constants are determined by fitting the 1H nuclear magnetic resonance (NMR) titration curves to give β1 and β2 values, which are used to characterize the diastereomeric and enantiomeric discriminating potentials of the hosts. Chirality 25:47–479, 2013. © 2013 Wiley Periodicals, Inc.

Published
2013
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19. Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

Author

Jérôme Lacour, Stéphane Grass, Pascal Dimitrov-Raytchev, Laure Guy, Alexandre Martinez, Elina Payet, Bastien Chatelet, and Jean-Pierre Dutasta

Subjects
Pharmacology, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Absolute configuration, Cationic polymerization, Diastereomer, 010402 general chemistry, 01 natural sciences, High-performance liquid chromatography, Catalysis, 0104 chemical sciences, 3. Good health, Analytical Chemistry, chemistry.chemical_compound, TRISPHAT, Drug Discovery, Moiety, Enantiomer, Chirality (chemistry), Spectroscopy
Abstract

The hemicryptophane racemate (±)-M-1, P-1 was optically resolved by semipreparative HPLC on Chiralpak IC column. The absolute configuration of each isolated enantiomer was established from the analysis of their electronic circular dichroism spectra. Enantiodifferentiation of the chiral cationic cage (±)-M-1, P-1 was evidenced in solution using Δ-TRISPHAT as chiral solvating agent, and the diastereomeric associations were observed in 1H and 31P NMR spectra. Chirality 24:1077–1081, 2012. © 2012 Wiley Periodicals, Inc.

Published
2012
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20. Remote Control of Helical Chirality: Thermodynamic Resolution of a Racemic Mixture of CTV Units by Remote Stereogenic Centers

Author

Véronique Dufaud, Jean-Pierre Dutasta, Vincent Robert, Lionel Joucla, Bastien Chatelet, Guillaume Pilet, Alexandre Martinez, Daniele Padula, Lorenzo Di Bari, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Dipartimento di Chimica e Chimica Industriale, University of Pisa - Università di Pisa, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
Models, Molecular, Stereochemistry, Supramolecular chemistry, Molecular Conformation, Catalysis, Crystallography, X-Ray, Molecular Structure, Polycyclic Compounds, Stereoisomerism, Thermodynamics, Cyclotriveratrylene, 010402 general chemistry, 01 natural sciences, Biochemistry, Stereocenter, chemistry.chemical_compound, Models, Physical and Theoretical Chemistry, Crystallography, 010405 organic chemistry, Chemistry, Organic Chemistry, Diastereomer, Molecular, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Enantiopure drug, X-Ray, Racemic mixture, Chirality (chemistry)
Abstract

International audience; Enantiopure hemicryptophanes designed from the cyclotriveratrylene (CTV) unit display remarkable properties in selective host–guest recognition or as supramolecular catalysts. The unprecedented control of the helical chirality of the CTV unit by remote stereogenic centers of a tren moiety is reported, providing an original access to this highly promising class of host molecules. Although the chiral centers and the CTV unit are separated by more than 10 Å, one single diastereomer is formed; the nature of the diastereoselective process is discussed and the procedure is exemplified using different enantiopure tren derivatives. This work also highlights the influence of the chirality of the CTV unit on the whole cage structure.

Published
2015
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21. Diastereoselective recognition of α-mannoside by hemicryptophane receptors

Author

Lorenzo Di Bari, Aline Schmitt, Alexandre Martinez, Daniele Padula, Bastien Chatelet, Jean-Pierre Dutasta, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Stereochemistry, Absolute configuration, Mannose, General Chemistry, Carbohydrate, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Enantiopure drug, chemistry, Galactose, Materials Chemistry, Receptor
Abstract

International audience; Four new enantiopure hemicryptophanes were synthesized and their absolute configuration was determined from experimental and calculated ECD spectra. Complexation properties of these receptors were studied toward six carbohydrate stereoisomers derived from glucose, galactose and mannose. All the receptors showed a better affinity for α-mannoside with association constants up to 2.5 × 103 M−1. One of the receptor can complex almost exclusively α-mannoside facing to α-galactoside.

Published
2015
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22. Catalytic Activity of an Encaged Verkade’s Superbase in a Base-Catalyzed Diels–Alder Reaction

Author

Alexandre Martinez, Véronique Dufaud, Bastien Chatelet, Jean-Pierre Dutasta, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Cycloaddition Reaction, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Superbase, Diastereomer, Stereoisomerism, Proazaphosphatrane, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Maleimides, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Pyrones, Organocatalysis, Organic chemistry, Thermodynamics, Stereoselectivity, Diels–Alder reaction
Abstract

International audience; Organocatalysis in a confined space has been performed through encapsulation of a proazaphosphatrane superbase in a hemicryptophane host. The resulting catalyst displays good to high catalytic activity in the base-catalyzed Diels–Alder reactions investigated. A comparison with the model superbase, which lacks a cavity, shows much higher diastereomeric excess with the encaged proazaphosphatrane for the reaction of 3-hydroxy-2-pyrone with N-methylmaleimide. The use of an encaged superbase as organocatalyst is unprecedented and highlights how the confinement may impact the stereoselectivity.

Published
2014
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23. Azaphosphatrane Organocatalysts in Confined Space: Cage Effect in CO2 Conversion

Author

Lionel Joucla, Alexandre Martinez, Véronique Dufaud, Bastien Chatelet, Jean-Pierre Dutasta, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Green chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical engineering, Organocatalysis, Organic chemistry, Surface modification, Cage effect, Cage, Confined space, Electronic properties
Abstract

International audience; The endohedral functionalization of a molecular cage by an azaphosphatrane unit has allowed for the creation of highly engineered catalytic cavities for efficient conversion of CO2 into cyclic carbonates. Strong structure/activity/stability correlations have been demonstrated by careful adjustment of the size, shape, and electronic properties of the hemicryptophane host.

Published
2014
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24. Role of pre-organization around the azaphosphatrane catalyst's active site in the conversion of CO2 to cyclic carbonates

Author

Véronique Dufaud, Bastien Chatelet, Vincent Robert, Jean-Pierre Dutasta, Erwann Jeanneau, Alexandre Martinez, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
biology, Chemistry, Process Chemistry and Technology, Cyclic carbonates, Active site, Homogeneous catalysis, General Chemistry, Azaphosphatranes, Catalysis, Styrene, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Epoxides, biology.protein, Organic chemistry, CO2 chemical valorization
Abstract

International audience; Various N-substituted azaphosphatranes have been prepared and successfully applied to the synthesis of styrene carbonates from CO2 and epoxides. Enhancement of the catalytic properties of the azaphosphatrane was achieved upon pre-organization of the active site through hydrogen-bonding.

Published
2014
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25. Improved hemicryptophane hosts for the stereoselective recognition of glucopyranosides

Author

Benjamin Bousquet, Aline Schmitt, Marion Valls, Elina Payet, Daniele Padula, Bastien Chatelet, Jean-Pierre Dutasta, Lorenzo Di Bari, Olivier Perraud, Alexandre Martinez, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Models, Molecular, Chemistry, Stereochemistry, Circular Dichroism, Proton Magnetic Resonance Spectroscopy, Organic Chemistry, Absolute configuration, Molecular Conformation, Stereoisomerism, Circular dichroism spectra, Biochemistry, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Sugar derivatives, Kinetics, Glucosides, Proton NMR, Molecule, Quantum Theory, Stereoselectivity, Titration, Polycyclic Compounds, Physical and Theoretical Chemistry
Abstract

International audience; Four new enantiomerically and diastereomerically pure hemicryptophane hosts (M-SSS-2/P-SSS-2 and M-RRR-2/P-RRR-2 pairs) were designed for the recognition of sugar derivatives. Their absolute configuration was determined from the circular dichroism spectra and DFT calculations. The host molecules were then used for the stereoselective recognition of glucopyranosides. Binding constants were obtained from 1H NMR titration experiments showing an increase of affinity for this class of receptors, associated with an improved diastereo- and enantio-differentiation.

Published
2014
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26. Immobilization of a N-substituted azaphosphatrane in nanopores of SBA-15 silica for the production of cyclic carbonates

Author

Bastien Chatelet, Alexandre Martinez, Véronique Dufaud, Lionel Joucla, Jean-Pierre Dutasta, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Thermogravimetric analysis, Materials science, Renewable Energy, Sustainability and the Environment, Infrared spectroscopy, Alkyne, General Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, Styrene oxide, Polymer chemistry, Click chemistry, Organic chemistry, General Materials Science, Epichlorohydrin, Hybrid material, Mesoporous material
Abstract

International audience; A novel N-substituted azaphosphatrane molecular precursor bearing an alkyne tether was synthesized using a multi-step strategy and covalently immobilized onto SBA-15 type silica through triazole linkages by means of the well-known click chemistry. The resulting hybrid material, [7]@SBA-15, was characterized well by methods appropriate to molecular species (e.g. solid state 13C, 31P and 29Si NMR, infrared spectroscopy and elemental analysis) as well as techniques more commonly associated with the characterization of mesoporous solids (nitrogen sorption isotherms, powder X-ray diffraction, TGA analysis). The catalytic activity of [7]@SBA-15 was then evaluated in the coupling of CO2 with two epoxides (styrene oxide and epichlorohydrin) and compared to its monotriazole modified AZAP molecular analog, 8. This work represents the first example of silica modified N-substituted azaphosphatrane for the production of cyclic carbonates.

Published
2014
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27. Azaphosphatranes as Structurally Tunable Organocatalysts for Carbonate Synthesis from CO2 and Epoxides

Author

Véronique Dufaud, Lionel Joucla, Jean-Pierre Dutasta, Alexandre Martinez, Bastien Chatelet, Kai C. Szeto, Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Reaction mechanism, Kinetic analysis, Carbonates, Ether, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Colloid and Surface Chemistry, Organophosphorus Compounds, Styrene oxide, Organic chemistry, Epichlorohydrin, Reaction conditions, Aza Compounds, Molecular Structure, 010405 organic chemistry, Chemistry, General Chemistry, Carbon Dioxide, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Carbonate, Epoxy Compounds
Abstract

International audience; Three azaphosphatranes were used as organocatalysts for the synthesis of cyclic carbonates from CO2 and epoxides. They proved to be efficient single-component, metal-free catalysts for the reaction of simple or activated epoxides (styrene oxide, epichlorohydrin, glycidyl methyl ether) with CO2 under mild reaction conditions, displaying high stability and productivity over several days of reaction. Substitution patterns on the catalyst were shown to affect activity and stability. Kinetic analysis allowed investigation of the reaction mechanism.

Published
2013
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28. Chiral discrimination of ammonium neurotransmitters by C₃-symmetric enantiopure hemicryptophane hosts

Author

Aline, Schmitt, Bastien, Chatelet, Solène, Collin, Jean-Pierre, Dutasta, and Alexandre, Martinez

Subjects
Ephedrine, Models, Molecular, Neurotransmitter Agents, Magnetic Resonance Spectroscopy, Molecular Structure, Ammonium Compounds, Polycyclic Compounds, Stereoisomerism
Abstract

Enantiopure hemicryptophanes efficiently discriminate chiral ammonium neurotransmitters. The ephedrine and norephedrine molecules associate with hemicryptophane hosts to form 1:1 and 1:2 host-guest complexes. Binding constants are determined by fitting the ¹H nuclear magnetic resonance (NMR) titration curves to give β₁ and β₂ values, which are used to characterize the diastereomeric and enantiomeric discriminating potentials of the hosts.

Published
2013

29. Absolute Configuration and Enantiodifferentiation of a Hemicryptophane Incorporating an Azaphosphatrane Moiety

Author

Elina, Payet, Pascal, Dimitrov-Raytchev, Bastien, Chatelet, Laure, Guy, Stephane, Grass, Jerome, Lacour, Jean-Pierre, Dutasta, Alexandre, Martinez, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Spectroscopie de l'atmosphère, Service de Chimie Quantique et Photophysique, Université libre de Bruxelles (ULB), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Chiral solvating agent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chiroptical properties, ddc:540, TRISPHAT, Absolute configuration, Hemicryptophane, Chiral separation
Abstract

International audience; The hemicryptophane racemate (±)-M-1, P-1 was optically resolved by semipreparative HPLC on Chiralpak IC column. The absolute configuration of each isolated enantiomer was established from the analysis of their electronic circular dichroism spectra. Enantiodifferentiation of the chiral cationic cage (±)-M-1, P-1 was evidenced in solution using Δ-TRISPHAT as chiral solvating agent, and the diastereomeric associations were observed in 1H and 31P NMR spectra. Chirality 24:1077–1081, 2012. © 2012 Wiley Periodicals, Inc.

Published
2012
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30. Shorter and modular synthesis of hemicryptophane-tren derivatives

Author

Jean-Pierre Dutasta, Laure-Lise Chapellet, Bastien Chatelet, Véronique Dufaud, Alexandre Martinez, Olivier Perraud, Pascal Dimitrov-Raytchev, Elina Payet, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Tris, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, business.industry, Organic Chemistry, Supramolecular chemistry, Modular design, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Vanillyl alcohol, chemistry, Molecule, Amine gas treating, Physical and Theoretical Chemistry, business
Abstract

International audience; Hemicryptophanes are host molecules with many applications as supramolecular catalysts or in ion selective recognition. A very convenient and efficient modular approach for the synthesis of hemicryptophane-tren (tren, tris(2-aminoethyl)-amine) derivatives has been developed. For instance, hemicryptophane 1 was synthesized at the gram scale in four steps from vanillyl alcohol compared to the previous seven-step procedure. The size, shape, and functionalities of the molecular cavity were also easily modified.

Published
2011
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31. Shorter and Modular Synthesis of Hemicryptophane-tren Derivatives.

Author

Bastien Chatelet, Elina Payet, Olivier Perraud, Pascal Dimitrov-Raytchev, Laure-Lise Chapellet, Véronique Dufaud, Alexandre Martinez, and Jean-Pierre Dutasta

Subjects
*ORGANIC synthesis, *SUPRAMOLECULAR chemistry, *CATALYSIS, *IONS, *AMINES, *ALCOHOLS (Chemical class)
Abstract

Hemicryptophanes are host molecules with many applications as supramolecular catalysts or in ion selective recognition. A very convenient and efficient modular approach for the synthesis of hemicryptophane-tren (tren, tris(2-aminoethyl)-amine) derivatives has been developed. For instance, hemicryptophane 1was synthesized at the gram scale in four steps from vanillyl alcohol compared to the previous seven-step procedure. The size, shape, and functionalities of the molecular cavity were also easily modified. [ABSTRACT FROM AUTHOR]

Published
2011
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32. Migration de l'interface du simulateur FarmSim de SWING vers JavaFX

Author

Neyret, Barnabé, Unité Mixte de Recherche sur l'Ecosystème Prairial - UMR (UREP), VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Ecole Centrale de Marseille, Bastien Chatelet, and Raphaël Martin

Subjects
Graphical user interface, Cycle de l'azote, Versioning, Gestion de versions, [SDE]Environmental Sciences, [INFO]Computer Science [cs], Carbon cycle, Interface utilisateur, Nitrogen cycle, Cycle du carbone
Abstract

Engineering school; I spent my internship in the unit in charge of grasslands' study, and I worked on FarmSim, a model of carbon and nitrogen storage inside farm plots. I modernized its graphical interface, while putting into practice processes like software versioning. I rened my idea of economic issues and working relationships through contact with other trainees..; J'ai passé mon stage dans l'unité chargée de l'étude des prairies, et travaillé sur le simulateur FarmSim 10, qui modélise le stockage de carbone et d'azote dans les parcelles d'une ferme. J'ai modernisé son interface graphique en assimilant les méthodes de l'unité comme le versionnement sur une forge logicielle. J'ai affiné ma conception des enjeux économiques et des relations de travail en entreprise au contact des autres stagiaires.

Published
2020

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