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1. Cover Feature: Cyanine‐ and Rhodamine‐Derived Alkynes for the Selective Targeting of Cancerous Mitochondria through Radical Thiol‐Yne Coupling in Live Cells (Chem. Eur. J. 45/2023)

Author: Köckenberger, Johannes, primary, Klemt, Insa, additional, Sauer, Caroline, additional, Arkhypov, Anton, additional, Reshetnikov, Viktor, additional, Mokhir, Andriy, additional, and Heinrich, Markus R., additional
Published: 2023
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2. Cyanine‐ and Rhodamine‐Derived Alkynes for the Selective Targeting of Cancerous Mitochondria via Radical Thiol‐Yne Coupling in Live Cells

Author: Köckenberger, Johannes, primary, Klemt, Insa, additional, Sauer, Caroline, additional, Arkhypov, Anton, additional, Reshetnikov, Viktor, additional, Mokhir, Andriy, additional, and Heinrich, Markus Rolf, additional
Published: 2023
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3. Cyanine‐ and Rhodamine‐Derived Alkynes for the Selective Targeting of Cancerous Mitochondria via Radical Thiol‐Yne Coupling in Live Cells

Author: Johannes Köckenberger, Insa Klemt, Caroline Sauer, Anton Arkhypov, Viktor Reshetnikov, Andriy Mokhir, and Markus Rolf Heinrich
Subjects: Organic Chemistry, General Chemistry, Catalysis
Published: 2023
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4. Cyanine‐ and Rhodamine‐Derived Alkynes for the Selective Targeting of Cancerous Mitochondria through Radical Thiol‐Yne Coupling in Live Cells.

Author: Köckenberger, Johannes, Klemt, Insa, Sauer, Caroline, Arkhypov, Anton, Reshetnikov, Viktor, Mokhir, Andriy, and Heinrich, Markus R.
Subjects: *RADICALS (Chemistry), *ALKYNES, *FLOW cytometry, *CANCER cells, *ORGANELLES
Abstract: Despite their long history and their synthetic potential underlined by various recent advances, radical thiol‐yne coupling reactions have so far only rarely been exploited for the functionalization of biomolecules, and no examples yet exist for their application in live cells ‐ although natural thiols show widespread occurrence therein. By taking advantage of the particular cellular conditions of mitochondria in cancer cells, we have demonstrated that radical thiol‐yne coupling represents a powerful reaction principle for the selective targeting of these organelles. Within our studies, fluorescently labeled reactive alkyne probes were investigated, for which the fluorescent moiety was chosen to enable both mitochondria accumulation as well as highly sensitive detection. After preliminary studies under cell‐free conditions, the most promising alkyne‐dye conjugates were evaluated in various cellular experiments comprising analysis by flow cytometry and microscopy. All in all, these results pave the way for improved future therapeutic strategies relying on live‐cell compatibility and selectivity among cellular compartments. [ABSTRACT FROM AUTHOR]
Published: 2023
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5. Cover Feature: Magnetic Slow Relaxation in a Metal-Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets (Chem. Eur. J. 27/2018)

Author: Huang, Gang, primary, Fernandez-Garcia, Guglielmo, additional, Badiane, Insa, additional, Camarra, Magatte, additional, Freslon, Stéphane, additional, Guillou, Olivier, additional, Daiguebonne, Carole, additional, Totti, Federico, additional, Cador, Olivier, additional, Guizouarn, Thierry, additional, Le Guennic, Boris, additional, and Bernot, Kevin, additional
Published: 2018
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6. Magnetic Slow Relaxation in a Metal-Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets

Author: Huang, Gang, primary, Fernandez-Garcia, Guglielmo, additional, Badiane, Insa, additional, Camarra, Magatte, additional, Freslon, Stéphane, additional, Guillou, Olivier, additional, Daiguebonne, Carole, additional, Totti, Federico, additional, Cador, Olivier, additional, Guizouarn, Thierry, additional, Le Guennic, Boris, additional, and Bernot, Kevin, additional
Published: 2018
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7. Cover Feature: Magnetic Slow Relaxation in a Metal-Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets (Chem. Eur. J. 27/2018)

Author: Federico Totti, Stéphane Freslon, Insa Badiane, Magatte Camarra, Thierry Guizouarn, Boris Le Guennic, Guglielmo Fernandez-Garcia, Kevin Bernot, Gang Huang, Olivier Guillou, Carole Daiguebonne, and Olivier Cador
Subjects: Lanthanide, Chemistry, Organic Chemistry, Relaxation (NMR), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Chemical physics, Magnet, Molecule, Metal-organic framework, Cover (algebra), 0210 nano-technology
Published: 2018
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8. Syntheses and Properties of Zinc and Calcium Complexes of Valinate and Isovalinate: Metal α-Amino Acidates as Possible Constituents of the Early Earth's Chemical Inventory.

Author: Strasdeit, Henry, Büsching, Insa, Behrends, Sabine, Saak, Wolfgang, and Barklage, Walter
Published: 2001
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9. Chiral Atropisomeric‐NHC Catechodithiolate Ruthenium Complexes for Z ‐Selective Asymmetric Ring‐Opening Cross Metathesis of Exo ‐Norbornenes

Author: Jennifer Morvan, Dylan Bouëtard, Lingyu Kong, Yajie Chou, Thomas Vives, Muriel Albalat, Thierry Roisnel, Christophe Crévisy, Paola Nava, Stéphane Humbel, Nicolas Vanthuyne, Hervé Clavier, Marc Mauduit, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We are grateful to the CNRS, the Ecole Nationale Supérieure de Chimie de Rennes, the Ecole Centrale Marseille and the Aix-Marseille Université. This work was supported by the Region Bretagne (ARED 2018 'Biometa' N° 601, grant to J.M.) and the Agence Nationale de la Recherche (ANR-20-CE07-0030 c-Résolu, grant to D.B.). L.K. and Y.C. thank the China Scholarship Council for a Ph.D. grant., and ANR-20-CE07-0030,cResolu,Accès direct à des complexes chiraux NHC-métal de transition : de nouvelles opportunités pour la catalyse asymétrique(2020)
Subjects: NHC, atropisomers, Organic Chemistry, Z-selectivity, olefin metathesis, [CHIM]Chemical Sciences, Enantioselectivity, General Chemistry, Catalysis
Abstract: International audience; A set of 16 chiral ruthenium complexes containing atropisomerically stable N-Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring-opening-cross metathesis (AROCM), the most effective chiral atrop BIAN-NHC Ru-catalyst (up to 97:3 er) was then converted to a Z-selective catechodithiolate complex. The latter proved to be highly efficient in Z-selective AROCM of exo-norbornenes affording valuable trans-cyclopentanes with excellent Z-selectivity (>98%) and high enantioselectivity (up to 96.5:3.5 er).
Published: 2023
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10. Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet‐Oxygen Production and Storage

Author: Christian Philouze, Guy Royal, Martial Boggio-Pasqua, Elise Lognon, Frédérique Loiseau, Saioa Cobo, Zakaria Ziani, Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE29-0012,Photochromics,Architectures Moléculaires Multi-Photochromes Innovantes pour la Production de NO et 1O2(2018)
Subjects: 010405 organic chemistry, Singlet oxygen, Organic Chemistry, Quantum yield, General Chemistry, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, 7. Clean energy, Acceptor, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Photochromism, chemistry.chemical_compound, chemistry, Cyclic voltammetry, Methylpyridinium, Absorption (electromagnetic radiation)
Abstract: International audience; A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methyl-pyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry and its properties were rationalized by theoretical calculations. The incorporation of both electron donor and withdrawing groups on the photochromic center allows i) an efficient photo-isomerization of the system when illuminated at low energy (quantum yield: Фc-o = 13.3% at λex.= 660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature and iii) the storage and production of singlet oxygen. The photo-isomerization mechanism was also investigated by spin-flip TD-DFT (SF-TD-DFT) calculations.
Published: 2021
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11. Trinuclear Cyanido‐Bridged [Cr 2 Fe] Complexes: To Be or not to Be a Single‐Molecule Magnet, a Matter of Straightness

Author: Jean-Pascal Sutter, Céline Pichon, Carine Duhayon, Nathalie Guihéry, Valentin Jubault, Nicolas Suaud, 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), Systèmes étendus et magnétisme (LCPQ) (SEM), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0007,AnisoChirMag,Anisotropie Optique au sein d'Aimants Moléculaires Chiraux: Vers une Lecture Optique de l'Orientation du Spin(2017), 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 et Physique Quantiques (LCPQ), 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)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Steric effects, 010405 organic chemistry, Chemistry, Magnetism, Organic Chemistry, Relaxation (NMR), General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Magnetization, Crystallography, Magnetic anisotropy, Pentagonal bipyramidal molecular geometry, Single-molecule magnets, Anisotropy, Moiety, Single-molecule magnet, Ab initio calculations, Pentagonal bipyramid
Abstract: International audience; Trinuclear systems of formula [{Cr(LN3O2Ph)(CN)2}2M(H2LN3O2R)] (M=MnII and FeII, LN3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M−N≡C linkages on the magnetic anisotropy of the FeII derivatives and in turn on their Single-Molecule Magnet (SMM) behaviors. The cyanido-bridged [Cr2M] derivatives were obtained by assembling trans-dicyanido CrIII complex [Cr(LN3O2Ph)(CN)2]− and divalent pentagonal bipyramid complexes [MII(H2LN3O2R)]2+ with various R substituents (R=NH2, cyclohexyl, S,S-mandelic) imparting different steric demand to the central moiety of the complexes. A comparative examination of the structural and magnetic properties showed an obvious effect of the deviation from straightness of the M−N≡C alignment on the slow relaxation of the magnetization exhibited by the [Cr2Fe] complexes. Theoretical calculations have highlighted important effects of the bending of the apical C−N−Fe linkages on both the magnetic anisotropy of the FeII center and the exchange interactions with the CrIII units.
Published: 2021
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12. Analysis of the Magnetic Coupling in a Mn(II)‐U(V)‐Mn(II) Single Molecule Magnet

Author: Sourav Dey, Gopalan Rajaraman, Hélène Bolvin, Indian Institute of Technology Bombay (IIT Bombay), Systèmes étendus et magnétisme (LCPQ) (SEM), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), ANR-17-EURE-0009,NanoX,Science et Ingénierie à l'Echelle Nano(2017), and ANR-17-CE06-0010,ACTIpNMR,déplacements de RMN paramagnétiques pour les actinides : au délà du modèle des lanthanides(2017)
Subjects: Organic Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Catalysis
Abstract: International audience; [{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA = tris(2-pyridylmethyl)amine and Mesaldien = N,N'-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014, 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d-5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [U V O2] + is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component JZ twice larger as the perpendicular one J ⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the JZ /J ⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding g S-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d-5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [U V O2] + 5f orbitals.
Published: 2022
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13. Ytterbium (II) Hydride as a Powerful Multielectron Reductant

Author: Iskander Douair, Scott A. Cameron, Laurent Maron, Mathew D. Anker, Georgia M. Richardson, Victoria University of Wellington, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Ytterbium, polyaromatic hydrocarbons, Hydrogen, Hydride, multielectron reduction, Organic Chemistry, naphthalene, Aromatization, chemistry.chemical_element, General Chemistry, Photochemistry, Catalysis, chemistry.chemical_compound, 7-cyclooctatetraene, Deprotonation, chemistry, ytterbium hydrides, Density functional theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Naphthalene
Abstract: International audience; A dimeric beta-diketiminato ytterbium(II) hydride affects both the two-electron aromatization of 1,3,5,7-cyclooctatetraene (COT) and the more challenging two-electron reduction of polyaromatic hydrocarbons, including naphthalene (E-0=-2.60 V). Confirmed by Density Functional Theory calculations, these reactions proceed via consecutive polarized Yb-H/C=C insertion and deprotonation steps to provide the respective ytterbium (II) inverse sandwich complexes and hydrogen gas. These observations highlight the ability of a simple ytterbium(II) hydride to act as a powerful two-electron reductant at room temperature without the necessity of an external electron to initiate the reaction and avoiding radicaloid intermediates.
Published: 2021
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14. Molecular Design of Silicon‐Containing Diazenes: Absorbance of E and Z Isomers in the Near‐Infrared Region

Author: Valery Sidorkin, Viatcheslav Jouikov, Evgeniya Doronina, Siberian Branch of the Russian Academy of Sciences (SB RAS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Russian Foundation for Basic Research. Grant Number: Grant No. 19-03-00143
Subjects: UV-Vis-NIR spectra, ab initio calculations, Organic Chemistry, silicon, [CHIM]Chemical Sciences, photoisomerization, General Chemistry, Imides, Azo Compounds, DFT, Catalysis, diazenes
Abstract: International audience; The effective use of photochromic systems based on azo compounds in a number of applications, especially biomedical and pharmacological ones, is impeded by the unresolved problem of their E⇆Z isomerization in the near-IR region, NIR (780-1400 nm). We have demonstrated at the TD-DFT, STEOM-DLPNO-CCSD and CASSCF-NEVPT2 levels of theory that the presence of a silylated diazene core -Si-N=N-Si- with three-, tetra- or five-coordinated silicon atoms practically guarantees the absorption of the E and Z forms of such derivatives in NIR and the amazing (185-400 nm) separation of their first absorption bands. In particular, the maximum λ(1) of the first n→π* band of the E isomer of azosilabenzene ASiB is at ∼1030 nm, while for the Z isomer λ(1) ≅1340 nm. Based on the found bistable azo compounds (ASiB, bis(silyl)- SiD and bis(silatranyl)- SaD diazenes) and their derivatives with E and Z absorption in NIR, unique photoswitches can be created for a number of applications, in particular, for photothermal therapy.
Published: 2022
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15. Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations

Author: Michele Tomasini, Lucia Caporaso, Jonathan Trouvé, Jordi Poater, Rafael Gramage‐Doria, Albert Poater, Universitat de Girona (UdG), Università degli Studi di Salerno = University of Salerno (UNISA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona (UB), ANR-19-CE07-0039,REMOTCAT,Fonctionalisation 'remote' des molecules par catalyse supramoleculaire(2019), and Agencia Estatal de Investigación
Subjects: Porphyrins, Catalitzadors d'iridi, Chemistry -- Data processing, Pyridines, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, enzyme mimics, General Chemistry, DFT calculations, Iridium, Química -- Informàtica, Catalysis, Iridium catalysts, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, C−H functionalization, Zinc, Química -- Simulació per ordinador, supramolecular catalysis, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chemistry -- Computer simulation, iridium
Abstract: Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C−H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C−B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states Institució Catalana de Recerca i Estudis Avançats. Grant Number: ICREA Academia 2019. Ministerio de Ciencia e Innovación. Grant Numbers: PGC2018-097722-B-I00, PID2019-106830GB-I00, MDM-2017-0767, PID2021-127423NB-I00 Open Access funding provided thanks to the CRUE-CSIC agreement with Wiley
Published: 2022
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16. Ru(II)‐Catalyzed Hydroarylation of in situ Generated 3,3,3‐Trifluoro‐1‐propyne by C−H Bond Activation: A Facile and Practical Access to β‐Trifluoromethylstyrenes

Author: Martin Vuagnat, Vincent Tognetti, Philippe Jubault, Tatiana Besset, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018), ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), and European Project: 758710,FarCatCH
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Catalysis
Abstract: International audience; In this study, a practical and straightforward synthesis of β-( E )-trifluoromethylstyrenes by ruthenium-catalyzed C-H bond activation was developed. The readily available and inexpensive 2-bromo-3,3,3-trifluoropropene (BTP), a non-ozone depleting reagent, was used as a reservoir of 3,3,3-trifluoropropyne. With this approach, the monofunctionalization of a panel of heteroarenes was possible in a safe and scalable manner (23 examples, up to 87% yield). Mechanistic investigations and density functional theory (DFT) calculations were also conducted to get a better understanding of the mechanism of this transformation. These studies suggested that 1) a cyclometallated ruthenium complex enabled the transformation, 2) this latter exhibited high efficiency in this transformation compared to the commercially available [RuCl 2 ( p -cymene)] 2 and 3) the mechanism proceeded through a bis-cyclometallated ruthenium intermediate for the carboruthenation step
Published: 2022
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17. Selective Iron Catalyzed Synthesis of N‐Alkylated Indolines and Indoles

Author: Jiajun Wu, Satawat Tongdee, Marie Cordier, Christophe Darcel, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes 1 CNRS China Fellowship Council
Subjects: indoline, Indoles, Alkylation, Iron, Organic Chemistry, Trifluoroethanol, General Chemistry, N-alkylation, Catalysis, Indole, Alcohols, Hydrogen Auto-transfer, [CHIM]Chemical Sciences, Hydrogen
Abstract: Whereas iron catalysts usually promote catalyzed C3-alkylation of indole derivatives via a borrowing-hydrogen methodology using alcohols as the electrophilic partners, this contribution shows how to switch the selectivity towards N-alkylation. Thus, starting from indoline derivatives, N-alkylation was efficiently performed using a tricarbonyl(cyclopentadienone) iron complex as the catalyst in trifluoroethanol in the presence of alcohols leading to the corresponding N-alkylated indoline derivatives in 31-99 % yields (28 examples). The one-pot, two-step strategy for the selective N-alkylation of indolines is completed by an oxidation to give the corresponding N-alkylated indoles in 31-90 % yields (15 examples). This unprecedented oxidation methodology involves an iron salt catalyst associated with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) and a stoichiometric amount of t-BuOOH at room temperature.
Published: 2022
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18. Computational Insights into Different Mechanisms for Ag‐, Cu‐, and Pd‐Catalyzed Cyclopropanation of Alkenes and Sulfonyl Hydrazones

Author: Laurent Maron, Yong Wu, Iskander Douair, Shanshan Cao, Xihe Bi, Northeast Normal University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), NSFC [21871043, 21961130376], Department of Science and Technology of Jilin Province [20180101185JC, 20190701012GH], and Fundamental Research Funds for the Central Universities [2412020FZ006]
Subjects: Sulfonyl, chemistry.chemical_classification, 010405 organic chemistry, Cyclopropanation, Alkene, Organic Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Cycloaddition, 0104 chemical sciences, Cyclopropane, carbenes, reaction mechanisms, chemistry.chemical_compound, chemistry, density functional calculations, hindered alkenes, silver, Diazo, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Carbene
Abstract: International audience; The [2+1] cycloaddition reaction of a metal carbene with an alkene can produce important cyclopropane products for synthetic intermediates, materials, and pharmaceutical applications. However, this reaction is often accompanied by side reactions, such as coupling and self-coupling, so that the yield of the cyclopropanation product of non-silver transition-metal carbenes and hindered alkenes is generally lower than 50 %. To solve this problem, the addition of a low concentration of diazo compound (decomposition of sulfonyl hydrazones) to alkenes catalyzed by either CuOAc or PdCl2 was studied, but side reactions could still not be avoided. Interestingly, however, the yield of cyclopropanation products for such hindered alkenes were as high as 99 % with AgOTf as a catalyst. To explain this unexpected phenomenon, reaction pathways have been computed for four different catalysts by using DFT. By combining the results of these calculations with those obtained experimentally, it can be concluded that the efficiency of the silver catalyst is due to the barrierless concerted cycloaddition step and the kinetic inhibition of side reactions by a high concentration of alkene.
Published: 2021
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19. (Trifluoromethylselenyl)methylchalcogenyl as Emerging Fluorinated Groups: Synthesis under Photoredox Catalysis and Determination of the Lipophilicity

Author: Kevin Grollier, Arnaud De Zordo-Banliat, Flavien Bourdreux, Guillaume Dagousset, Emmanuel Magnier, Thierry Billard, Bruce Pégot, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'Etude et de Recherche Multimodal Et Pluridisciplinaire en imagerie du vivant (CERMEP - imagerie du vivant), Université de Lyon-Université de Lyon-CHU Grenoble-Hospices Civils de Lyon (HCL)-CHU Saint-Etienne-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), and ANR-18-CE07-0039,SAFA,Selenium et Fluor Associés: le mariage de 2 stars(2018)
Subjects: Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Decarboxylation, Organic Chemistry, Photoredox catalysis, chemistry.chemical_element, General Chemistry, Flow chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Lipophilicity, Fluorine, [CHIM]Chemical Sciences, Molecule, Surface modification, Oxidation-Reduction
Abstract: International audience; The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two-step strategy based on a metal-free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88% which raised to 98% in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physico-chemical characterization of these emerging groups was performed by determining their Hansch-Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95%. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives.
Published: 2021
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20. Synthesis and Properties of Higher Nuclearity Polyazanes

Author: Maurice Médebielle, Emmanuel Lacôte, Thomas Criton, Debora Vilona, Lionel Joucla, Elise Dumont, Guy Jacob, Lacôte, Emmanuel, Laboratoire Hydrazines et Composés Energetiques Polyazotés (LHCEP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-HERAKLES - SAFRAN-Centre National d'Études Spatiales [Toulouse] (CNES)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, ArianeGroup, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon), Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), and École normale supérieure - Lyon (ENS Lyon)
Subjects: Molecular model, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Reducing agent, Organic Chemistry, chemistry.chemical_element, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Nitrogen, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Reagent, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Diazo, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Polyazanes (that is, higher nuclearity homologues of hydrazines) with increasing numbers of bound nitrogen atoms (from 3 to 5) were prepared via additions of lower order polyazanes to diazo reagents, including the first pentazane ever described. A structure was obtained. It was shown that the polynitrogen chains adopt a helical conformation. DFT modeling shows that the arrangement subsists in solution. While the polyazanes are all reducing agents, they become less so with the increasing number of nitrogens.
Published: 2021
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21. Study of Carbamoyl Fluoride: Synthesis, Properties and Applications

Author: Clémence Bonnefoy, Emmanuel Chefdeville, Christian Tourvieille, Armen Panossian, Gilles Hanquet, Frédéric Leroux, Fabien Toulgoat, Thierry Billard, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre d'Etude et de Recherche Multimodal Et Pluridisciplinaire en imagerie du vivant (CERMEP - imagerie du vivant), Université de Lyon-Université de Lyon-CHU Grenoble-Hospices Civils de Lyon (HCL)-CHU Saint-Etienne-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Billard, Thierry
Subjects: Fluorides, Fluorine Radioisotopes, Radiochemistry, Halogenation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, Catalysis
Abstract: International audience; Carbamoyl fluoride is a fluorinated group which, to this date, remains underexplored, probably due to the lack of data concerning their properties. In this paper, a study of carbamoyl fluoride is proposed. Stability studies, in particular under physiological conditions, and lipophilicity measurement have been performed. A new easy, safe, inexpensive and metal-free synthesis method has also been described. Finally, a potential use in radiochemistry through a 18 F/ 19 F isotopic exchange has been demonstrated.
Published: 2022
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22. Methyl Viologens of Bis‐(4’‐Pyridylethynyl)Arenes – Structures, Photophysical and Electrochemical Studies, and their Potential Application in Biology

Author: Goutam Kumar Kole, Marta Košćak, Anissa Amar, Dragomira Majhen, Ksenija Božinović, Zlatko Brkljaca, Matthias Ferger, Evripidis Michail, Sabine Lorenzen, Alexandra Friedrich, Ivo Krummenacher, Michael Moos, Holger Braunschweig, Abdou Boucekkine, Christoph Lambert, Jean‐François Halet, Ivo Piantanida, Klaus Müller‐Buschbaum, Todd B. Marder, University of Würzburg = Universität Würzburg, Institut Ruđer Bošković (IRB), Université Mouloud Mammeri [Tizi Ouzou] (UMMTO), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Justus-Liebig-Universität Gießen = Justus Liebig University (JLU), Alexander von Humboldt-Stiftung, Julius-Maximilians-Universität Würzburg, Croatian Science Foundation. Grant Number: IP-2018-01-5475, and Grand Équipement National De Calcul Intensif. Grant Number: 2021-080649
Subjects: Anthracenes, Paraquat, Methyl Viologen, Two-photon Absorption, Singlet Oxygen, DNA/RNA Binding, Cell Imaging, Molecular Structure, Singlet oxygen, Organic Chemistry, Benzene, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, DNA, General Chemistry, Catalysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, cell imaging, ddc:540, Humans, RNA, two-photon absorption, Biology
Abstract: A series of bis‐(4’‐pyridylethynyl)arenes (arene=benzene, tetrafluorobenzene, and anthracene) were synthesized and their bis‐N‐methylpyridinium compounds were investigated as a class of π‐extended methyl viologens. Their structures were determined by single crystal X‐ray diffraction, and their photophysical and electrochemical properties (cyclic voltammetry), as well as their interactions with DNA/RNA were investigated. The dications showed bathochromic shifts in emission compared to the neutral compounds. The neutral compounds showed very small Stokes shifts, which are a little larger for the dications. All of the compounds showed very short fluorescence lifetimes (
Published: 2022
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23. Naphthyl‐Fused Phosphepines: Luminescent Contorted Polycyclic P‐Heterocycles

Author: Denis Tondelier, Thomas Delouche, Thierry Roisnel, Zoltán Benkő, Pierre-Antoine Bouit, Réka Mokrai, Bernard Geffroy, Muriel Hissler, László Nyulászi, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de physique des interfaces et des couches minces [Palaiseau] (LPICM), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Budapest University of Technology and Economics [Budapest] (BME), 16-CE05-0003-01, 17-CE09-0020, Agence Nationale de la Recherche, ANR-17-CE09-0020,FluoHyb,Nouveaux matériaux hybrides fluorescents basés sur le concept de l'émission induite par agrégation de chromophores organiques greffés sur des nanoparticules inorganiques.(2017), ANR-16-CE05-0003,Heterographene,Synthèse et étude des propriétés électroniques de polycycles aromatiques contenant des hétéroatomes(2016), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and MTA-BME Research Group of Technical Analytical Chemistry
Subjects: optical properties, Steric effects, Substitution reaction, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, Oxide, P-heterocycles, General Chemistry, organic light-emitting diodes, pi-conjugated systems, 010402 general chemistry, Photochemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, chemistry, OLED, Cyclic voltammetry, Luminescence, density function calculations, Pnictogen
Abstract: International audience; This article presents the synthesis of a new family of naphthyl-fused phosphepines through Ni-mediated C-C coupling. Interestingly, the chlorophosphine oxide intermediate shows strong resistance toward oxidation/hydrolysis owing to a combination of steric hindrance and pnictogen interactions. However, it can undergo substitution reactions under specific conditions. The optical/redox properties and the electronic structure of these new π-systems were studied experimentally (UV/Vis absorption, emission, cyclic voltammetry) and computationally (TD-DFT calculations, NICS investigation). Taking advantage of the luminescence of these derivatives, a blue-emitting OLED has been prepared, highlighting that these novel π-conjugated P-heterocycles appear to be promising building blocks for solid-state lighting applications.
Published: 2020
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24. Cover Picture.

Author: Strasdeit, Henry, Büsching, Insa, Behrends, Sabine, Saak, Wolfgang, and Barklage, Walter
Published: 2001
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25. N‐Heterocyclic Carbene‐Catalyzed Formal [6+2] Annulation Reaction via Cross‐Conjugated Aza‐Trienolate Intermediates

Author: Akkattu T. Biju, Tatiana Besset, Arghya Ghosh, Kuruva Balanna, Thomas Poisson, Krishnaprasad Madica, Garima Jindal, Subrata Mukherjee, Department of Theoretical and Applied Mechanics [Ithaca], Cornell University [New York], Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Annulation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, Organic Chemistry, General Chemistry, Conjugated system, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Organocatalysis, Electrophile, [CHIM]Chemical Sciences, Reactivity (chemistry), Carbene
Abstract: International audience; The diverse reactivity of N‐heterocyclic carbenes (NHCs) in organocatalysis is due to the possibility of different modes of action. Although NHC‐bound enolates and dienolates are known, the related NHC‐bound cross‐conjugated aza‐trienolates remain elusive. Herein, we demonstrate the NHC‐catalyzed formal [6+2] annulation of nitrogen‐containing heterocyclic aldehydes with α,α,α‐trifluoroacetophenones leading to the formation of versatile pyrrolooxazolones (29 examples). The catalytically generated cross‐conjugated aza‐trienolates (aza‐fulvene type) underwent smooth [6+2] annulation with electrophilic ketones to afford the product in moderate to good yields under mild conditions. Preliminary DFT studies on the mechanism are also provided.
Published: 2019
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26. Copper‐Catalyzed Enantioselective Formation of C−CF 3 Centers from β‐CF 3 ‐Substituted Acrylates and Acrylonitriles

Author: Xavier Pannecoucke, Maria V. Ivanova, Thomas Poisson, Philippe Jubault, Pauline Poutrel, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, hydrides, asymmetric catalysis, chemistry.chemical_element, reduction, General Chemistry, trifluoromethyl group, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Copper, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, copper, Functional group, Copper catalyzed, [CHIM]Chemical Sciences
Abstract: International audience; The catalytic asymmetric synthesis of β‐trifluoromethylated esters or nitriles is reported. The use of an in situ formed chiral Cu−H complex allowed the enantioselective reduction of β‐trifluoromethylated acrylates or acrylonitriles. The reaction proceeds smoothly affording the corresponding enantioenriched products in good to excellent yields and outstanding enantioselectivities (up to 98 % ee). The mechanism of the reaction was studied, and a plausible reaction pathway was suggested accordingly. Finally, the versatility of the products was highlighted through functional group manipulations.
Published: 2019
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27. Dearomatization of 3‐Nitroindoles with Highly γ‐Functionalized Allenoates in Formal (3+2) Cycloadditions

Author: Léo Birbaum, Isabelle Chataigner, Xavier Moreau, Guillaume Vincent, Hélène Gérard, Hassan Oulyadi, Laurent Gillard, Michaël De Paolis, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Lavoisier de Versailles (ILV), and Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Reaction mechanism, Annulation, 010405 organic chemistry, Biomolecule, Organic Chemistry, Sequence (biology), General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Density functional calculation, [CHIM]Chemical Sciences, Phosphine
Abstract: International audience; 3‐Nitroindoles are easily reacted with highly substituted γ‐allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3‐nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α‐regioisomers exclusively. DFT computations shed light on this multi‐step reaction mechanism and on the selectivities observed in the sequence.
Published: 2019
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28. Ambipolar Discotic Liquid Crystals Built Around Platinum Diimine‐Dithiolene Cores

Author: Marc Fourmigué, Franck Camerel, Corinne Lagrost, Grégory Albert, Frédéric Barrière, Olivier Jeannin, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Ambipolar, 010405 organic chemistry, Ligand, Chemistry, Discotic liquid crystal, Mesogen, Organic Chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Coordination complex, Coordination Chemistry, Crystallography, Charge transfer, Liquid crystal, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Platinum diimine dithiolene, Platinum, Diimine
Abstract: International audience; Platinum diimine dithiolene complexes bearing mesogenic groups on one or both ligands have been prepared through an original ligand metathesis reaction to introduce the dithiolene ligand. The neutral diimine ligands, the intermediate platinum dichloride diimine complexes and the target compounds were characterized by a combination of electronic (electrochemistry, absorption and emission spectroscopy, DFT calculations) and structural (SAXS, DSC) tools. Several novel liquid crystalline platinum diimine-dithiolene were identified over a large temperature range, furthermore endowed with ambipolar properties, associated with the high reversibility of both oxidation and reduction processes.
Published: 2019
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29. Redox‐Active Chiroptical Switching in Mono‐ and Bis‐Iron Ethynylcarbo[6]helicenes Studied by Electronic and Vibrational Circular Dichroism and Resonance Raman Optical Activity

Author: Markus Reiher, Monika Srebro-Hooper, Francisco J. Ramírez, Juan T. López Navarrete, Jeanne Crassous, Florian Krausbeck, Thomas Weymuth, Belén Nieto-Ortega, Juan Casado, Chengshuo Shen, Jochen Autschbach, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Uniwersytet Jagielloński w Krakowie = Jagiellonian University (UJ), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Universidad de Málaga [Málaga] = University of Málaga [Málaga], University at Buffalo [SUNY] (SUNY Buffalo), State University of New York (SUNY), 12-BS07-0004-METALHEL-01, Agence Nationale de la Recherche, 200020_169120, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, CHE-1560881, National Science Foundation, FEDER CTQ2015-69391-P, MINECO of the Government of Spain, ANR-12-BS07-0004,MetalHel,Dérivés hélicéniques multifonctionnels à base de métaux(2012), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Circular dichroism, redox activity, RROA, Organometallic helicenes, Chiroptical switching, Redox activity, VCD, 010405 organic chemistry, Organic Chemistry, Resonance, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Spectral line, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Helicene, chemistry, Vibrational circular dichroism, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Raman optical activity, organometallic helicenes, chiroptical switching, Spectroscopy, Chirality (chemistry)
Abstract: International audience; Introducing one or two alkynyl-iron moieties onto a carbo[6]helicene results in organometallic helicenes (2 a,b) that display strong chiroptical activity combined with efficient redox-triggered switching. The neutral and oxidized forms have been studied in detail by electronic and vibrational circular dichroism, as well as by Raman optical activity (ROA) spectroscopy. The experimental results were analyzed and spectra were assigned with the help of first-principles calculations. In particular, a recently developed method for ROA calculations under resonance conditions has been used to study the intricate resonance effects on the ROA spectrum of mono-iron ethynylhelicene 2 a.
Published: 2018
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30. Isolated Collagen Mimetic Peptide Assemblies Have Stable Triple-Helix Structures

Author: Clothilde Comby-Zerbino, Mathilde Bouakil, Fabien Chirot, Jean-Christophe Poully, Mathieu Lalande, Philippe Dugourd, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Institut Lumière Matière [Villeurbanne] (ILM), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon, ANABIO-MS - Analyse biomoléculaire par spectrométrie de masse - Biological Analysis by Mass Spectrometry, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), CNRS is acknowledged for funding through the French GDR EMIE. M.L. and J.C.P. thank the 'Region Normandie' for a Ph.D. grant and for funding through the IRHEMME project (agreement #15P02908-15P02909). The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Program (FP7/2007-2013 Grant agreement No. 320659)., European Project: 0320659(2003), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: collagen, Proline, Hydroxylation, 010402 general chemistry, 01 natural sciences, Protein Structure, Secondary, Catalysis, Hydroxyproline, chemistry.chemical_compound, Biomimetic Materials, Tandem Mass Spectrometry, triple helix, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Phase (matter), [CHIM]Chemical Sciences, Molecule, structure, Protein Stability, 010405 organic chemistry, Organic Chemistry, Hydrogen Bonding, Stereoisomerism, General Chemistry, stability, 0104 chemical sciences, Solvent, chemistry, peptides, Biophysics, Stoichiometry, Triple helix
Abstract: International audience; The origin of the triple-helix structure and high stability of collagen has been debated for many years. As models of the triple helix and building blocks for new biomaterials, collagen mimetic peptide (CMP) assemblies have been deeply studied in the condensed phase. In particular, it was found that hydroxylation of proline, an abundant post-translational modification in collagen, increases its stability. Two main hypotheses emerged to account for this behavior: 1) intra-helix stereoelectronic effects, and 2) the role of water molecules H-bound to hydroxyproline side-chains. However, in condensed-phase investigations, the influence of water cannot be fully removed. Therefore, we employed a combination of tandem ion mobility and mass spectrometries to assess the structure and stability of CMP assemblies in the gas phase. These results show a conservation of the structure and stability properties of triple helix models in the absence of solvent, supporting an important role of stereoelectronic effects. Moreover, evidence that small triple helix assemblies with controlled stoichiometry can be studied in the gas phase is given, which opens new perspectives in the understanding of the first steps of collagen fiber growth.
Published: 2018
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31. Monomeric Rare-Earth Metal Silyl-Thiophosphinoyl-Alkylidene Complexes: Synthesis, Structure, and Reactivity

Author: Yan Yang, Laurent Maron, Li Xiang, Yaofeng Chen, Weiqing Mao, Xuebing Leng, Jian Fang, Chen Wang, Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences [Beijing] (CAS), Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Natural Science Foundation of China [21732007, 21325210], Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000], Program of Shanghai Academic Research Leader [18XD1404900], and HPCs CALcul en Midi-Pyrenees (CALMIP-EOS grant) [1415]
Subjects: Reaction mechanism, 010405 organic chemistry, Chemistry, Ligand, Metal ions in aqueous solution, Organic Chemistry, General Chemistry, 010402 general chemistry, Triple bond, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, visual_art, visual_art.visual_art_medium, Phenyl group, Reactivity (chemistry), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], density functional calculations, insertion, multiple bonds, rare earths, X-ray diffraction, Bond cleavage
Abstract: International audience; A series of monomeric rare-earth metal silyl-thiophosphinoyl-alkylidene complexes [LLn{C(SiR3)PPh2S}] (5: Ln=Lu, R=Me; 6: Ln=Lu, R=Ph; 7: Ln=Y, R=Me; 8: Ln=Y, R=Ph; 9: Ln=Sm, R=Ph; 10: Ln=Sm, R=Me; 11: Ln=La, R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH2CH2N(Me)(2))](-), DIPP=2,6-(iPr)(2)C6H3) have been synthesized and structurally characterized. The influences of rare-earth metal ions, ancillary ligands, and alkylidene groups on the reactivity of complexes 5-11 and the related scandium complexes [LSc{C(SiR3)PPh2S}] (1: R=Me; 2: R=Ph) and [LSc{C(SiR3)PPh2S}] (3: R=Me; 4: R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH2CH2N(iPr)(2))](-)) have been studied. Reactions of these rare-earth metal alkylidene complexes with PhCN give four kinds of products, the formation of which is dependent on the rare-earth metal ions, ancillary ligands, and alkylidene groups of the complexes. In the reactions with tBuNC, unusual C-P bond cleavage of the alkylidene group and CC triple bond formation occur. Complexes 10 and 11 also react with PhSiH3 to form hydrides, which subsequently undergo Ln-H addition to the C=N bond of the ancillary ligand L. DFT calculations have been used to analyze the bonding in complex 10, which exhibits a polarized three centers Sm-C-P interaction, and to rationalize the reactivity by computing reaction mechanisms. The difference in reactivity of PhCN and tBuNC is due to the electron density delocalization that is enabled by the phenyl group rather than the tBu group.
Published: 2018
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32. Multivalent Metallosupramolecular Assemblies as Effective DNA Binding Agents

Author: Sébastien Ulrich, Xiao-Yu Cao, Yannick Bessin, Wojciech Drożdż, Jean-Marie Lehn, Virginie Gervais, Artur R. Stefankiewicz, Anna Walczak, Centre de Biochimie Structurale [Montpellier] (CBS), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire d'Ingénierie des Systèmes Biologiques et des Procédés (LISBP), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de la Recherche Agronomique (INRA), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Adam Mickiewicz University in Poznań (UAM), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Recherche Agronomique (INRA)-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)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_element, Antineoplastic Agents, Zinc, Calorimetry, Crystallography, X-Ray, 010402 general chemistry, 01 natural sciences, Catalysis, Coordination complex, chemistry.chemical_compound, Cations, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Gel electrophoresis, 010405 organic chemistry, Organic Chemistry, Cationic polymerization, Isothermal titration calorimetry, DNA, General Chemistry, Nuclear magnetic resonance spectroscopy, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, chemistry, Self-assembly
Abstract: We report the implementation of coordination chemistry onto the generation of new types of metallosupramolecular complexes with laterally appended cationic moieties for DNA binding in buffered aqueous media. Utilization of an N,N,O-type coordination pocket along with an octahedral zinc(II) metal ion allowed us to obtain mono- and tetranuclear complexes in both solution and solid state, as confirmed by NMR spectroscopy and single-crystal X-ray diffraction, respectively. By using isothermal titration calorimetry and gel electrophoresis, multiply charged cationic assemblies were observed to effectively bind to DNA through multivalent electrostatic interactions. Furthermore, we observed a correlation between the multivalency of the compounds employed and the effectiveness of DNA binding.
Published: 2018
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33. Telescoping Reactions with Trifluorodiazoethane-Derived Aza-Wittig Reagents and Allenyl esters

Author: Jun-An Ma, Dominique Cahard, Yan Zheng, Fa-Guang Zhang, Yi-Quiang Tian, Jun-Liang Zeng, Tianjin University (TJU), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Reaction mechanism, 010405 organic chemistry, Chemistry, Organic Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Acetic acid, chemistry.chemical_compound, Reagent, Wittig reaction, [CHIM]Chemical Sciences, Diazo, Phosphine
Abstract: International audience; A telescoping process involving the consecutive addition of four reagents (trifluorodiazoethane, phosphine, allenyl ester, and acetic acid) into a single reactor was developed for the novel functionalization of allenyl esters. First, new phosphazenes derived from trifluorodiazoethane and phosphines were generated and reacted with allenyl esters to give unexpected α‐iminophosphoranes through the creation of C=P, C=N, and C−H bonds at the α‐, β‐, and γ‐carbon atoms, respectively, of the allenyl esters. The α‐iminophosphoranes did not react with aldehydes in a classic Wittig reaction, but instead β‐enamino esters were obtained. The overall sequence of reactions offered a formal hydrohydrazonation of allenyl esters. The method was extended to other related diazo compounds and applied to the preparation of novel 5‐pyrazolone derivatives. Not only is the telescoping process described herein an effective approach for truncating the multistep synthesis, but also each step has been dissected to understand and support the reaction mechanisms.
Published: 2018
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34. Dianionic Carbon-Bridged Scandium-Copper/Silver Heterobimetallic Complexes: Synthesis, Bonding, and Reactivity

Author: Chen Wang, Jian Fang, Xuebing Leng, Li Xiang, Yan Yang, Laurent Maron, Yaofeng Chen, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences [Beijing] (CAS), National Natural Science Foundation of China [21325210, 21732007], and Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000]
Subjects: chemistry.chemical_classification, Addition reaction, Double bond, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, General Chemistry, Reaction intermediate, 010402 general chemistry, 01 natural sciences, Copper, Catalysis, 0104 chemical sciences, Metal, Transmetalation, chemistry, visual_art, Polymer chemistry, visual_art.visual_art_medium, alkylidenes, cooperative effects, density functional calculations, heterometallic, scandium, Reactivity (chemistry), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Scandium
Abstract: International audience; Alkylidene-bridged scandium-copper/silver heterobimetallic complexes were synthesized and structurally characterized. The complexes contain different Sc-C and M-C (M=Cu-I, Ag-I) bonds. The reactivity of the scandium-copper heterobimetallic complex was also studied, which reveals that the heterobimetallic complex is a reaction intermediate for the transmetalation of akylidene group from Sc-III to Cu-I. The scandium-copper heterobimetallic complex also undergoes an addition reaction with CO, resulting in the formation of a new C=C double bond. DFT calculations were used to study the bonding and the subsequent reactivity with CO of the scandium-copper heterobimetallic complex. It clearly demonstrates a cooperative effect between the two metal centers through the formation of a direct Sc center dot center dot center dot Cu interaction that drives the reactivity with CO.
Published: 2018
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35. N−C Axially Chiral Anilines: Electronic Effect on Barrier to Rotation and A Remote Proton Brake

Author: Osamu Kitagawa, Christian Roussel, Hiroshi Hasegawa, Elsa Caytan, Ryuichi Morisawa, Satoshi Yokojima, Yumiko Iwasaki, Nicolas Vanthuyne, Shibaura Institute of Technology, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), JSPS KAKENNHI [C17K08220], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Proton, 010405 organic chemistry, Chemistry, Aryl, amines, Organic Chemistry, Protonation, General Chemistry, Electron, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, Axial chirality, density functional calculations, electronic effect, Electronic effect, proton brake, Phenyl group, axial chirality, Axial symmetry
Abstract: International audience; N-Aryl-N-methyl-2-tert-butyl-6-methylaniline derivatives exhibit a rotationally stable N-C axially chiral structure and the rotational barriers around an N-C chiral axis increased with the increase in electron-withdrawing character of para-substituent on the aryl group. X-ray crystal structural analysis and the DFT calculation suggested that the considerable change of the rotational barriers by the electron effect of para-substituents is due to the disappearance of resonance stabilization energy caused by the twisting of para-substituted phenyl group in the transition state. This structural property of the N-C axially chiral anilines was employed to reveal a new acid-decelerated molecular rotor caused by the protonation at the remote position (remote proton brake).
Published: 2018
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36. A Unique (3+2) Annulation Reaction between Meldrum's Acid and Nitrones: Mechanistic Insight by ESI-IMS-MS and DFT Studies

Author: Carlos Afonso, Etienne Pair, Clisy Maganga, Marie Hubert-Roux, Corinne Loutelier-Bourhis, Vincent Tognetti, Nicolas Lespes, Marie Bretier, Laurent Joubert, Vincent Levacher, Jean-François Brière, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Annulation, 010405 organic chemistry, Electrospray ionization, Organic Chemistry, Protonation, General Chemistry, 010402 general chemistry, Meldrum's acid, Mass spectrometry, 01 natural sciences, Catalysis, 0104 chemical sciences, Nitrone, chemistry.chemical_compound, chemistry, Computational chemistry, Organocatalysis, [CHIM]Chemical Sciences, Reactivity (chemistry)
Abstract: International audience; The fragile intermediates of the domino process leading to an isoxazolidin‐5‐one, triggered by unique reactivity between Meldrum's acid and an N‐benzyl nitrone in the presence of a Brønsted base, were determined thanks to the softness and accuracy of electrospray ionization mass spectrometry coupled to ion mobility spectrometry (ESI‐IMS‐MS). The combined DFT study shed light on the overall organocatalytic sequence that starts with a stepwise (3+2) annulation reaction that is followed by a decarboxylative protonation sequence encompassing a stereoselective pathway issue.
Published: 2018
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37. Alkyl Triarylstannanecarbodithioates: Synthesis, Crystal Structures, and Efficiency in RAFT Polymerization

Author: Stéphane Mazières, Nathalie Saffon-Merceron, Ihor Kulai, Zoia Voitenko, Mathias Destarac, Interactions moléculaires et réactivité chimique et photochimique (IMRCP), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), National Taras Shevchenko University of Kiev, Anthropologie Moléculaire et Imagerie de Synthèse (AMIS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Fédération de Recherche Fluides, Energie, Réacteurs, Matériaux et Transferts (FERMAT), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), P3R - Polymères de Précision par Procédés Radicalaires (P3R), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées
Subjects: chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Chain transfer, General Chemistry, Raft, Nuclear magnetic resonance spectroscopy, Polymer, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, End-group, chemistry, Polymerization, Polymer chemistry, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, ComputingMilieux_MISCELLANEOUS, Alkyl
Abstract: Eight alkyl triarylstannanecarbodithioates were synthesized starting from the corresponding triarylstannyl chlorides. They were fully characterized by IR and 1 H, 13 C, and 119 Sn NMR spectroscopy and mass spectrometry. Their solid-state structures and geometric parameters were determined and compared to those of other classes of thiocarbonylthio compounds. These new organotin derivatives are efficient reversible chain-transfer agents for reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and n-butyl acrylate (BA), with controlled number-average molecular weights and narrow dispersities (Ð
Published: 2017
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38. Coupling and Dearomatization of Pyridines at a Transient η2 -Cyclopropene/Bicyclobutane Zirconocene Complex

Author: Chiara Dinoi, Laure Vendier, Michel Etienne, Quentin Dufrois, Nuria Romero, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, 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 physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (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 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), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: pyridine, [PHYS]Physics [physics], 010405 organic chemistry, Stereochemistry, Ligand, Organic Chemistry, zirconium, General Chemistry, cyclopropene, coupling reactions, Cyclopropene, 010402 general chemistry, 01 natural sciences, Catalysis, Coupling reaction, 0104 chemical sciences, Cyclopropane, chemistry.chemical_compound, Stereospecificity, chemistry, Pyridine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Selectivity, cyclopropyl, Bicyclobutane
Abstract: bibtex: ISI:000414633200027 bibtex\location:'POSTFACH 101161, 69451 WEINHEIM, GERMANY',publisher:'WILEY-V C H VERLAG GMBH',type:'Article',affiliation:'Etienne, M (Reprint Author), CNRS, LCC, 205 Route Narbonne,BP44099, F-31077 Toulouse, France. Etienne, M (Reprint Author), Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France. Romero, Nuria; Dufrois, Quentin; Vendier, Laure; Dinoi, Chiara; Etienne, Michel, CNRS, LCC, 205 Route Narbonne,BP44099, F-31077 Toulouse, France. Romero, Nuria; Dufrois, Quentin; Vendier, Laure; Dinoi, Chiara; Etienne, Michel, Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France. Romero, Nuria, Univ Autonoma Barcelona, Dept Quim, Cerdanyola Del Valles Ba 08193, Spain. Dinoi, Chiara, LPCNO INSA, 135 Ave Rangueil, F-31077 Toulouse, France.','author-email':'michel.etienne@lcc-toulouse.fr',da:'2018-12-05','doc-delivery-number':'FM0EI',eissn:'1521-3765','funding-acknowledgement':'MENESR [ANR-11-BS07-0009]; COST Action CHAOS [CA15106]','funding-text':'We thank the MENESR for a PhD grant to QD, the ANR (Green-LAkE project; ANR-11-BS07-0009) and COST Action CHAOS (CA15106) for support.','journal-iso':'Chem.-Eur. J.','keywords-plus':'AROMATIC N-HETEROCYCLES; CH BOND ACTIVATION; CRYSTAL-STRUCTURES; ALKYL COMPLEXES; H BONDS; METAL; CHEMISTRY; ETA(2)-CYCLOPROPENE; ORGANOZIRCONIUM; NIOBIUM','number-of-cited-references':'42','orcid-numbers':'Romero, Nuria/0000-0002-2704-7779 Vendier, Laure/0000-0002-7111-9258 Etienne, Michel/0000-0002-1099-3232','research-areas':'Chemistry','researcherid-numbers':'Romero, Nuria/A-9756-2016','times-cited':'0','unique-id':'ISI:000414633200027','usage-count-last-180-days':'4','usage-count-since-2013':'12','web-of-science-categories':'Chemistry, Multidisciplinary'\; International audience; This paper reports on stereospecific coupling reactions between an (2)-cyclopropene ligand and pyridine derivatives, which are preferred to alternative C-H bond activation reactions. The dicyclopropylzirconocene complex [Cp2Zr(c-C3H5)(2)](1) eliminates cyclopropane to generate the (2)-cyclopropene/bicyclobutane intermediate [Cp2Zr((2)-c-C3H4)](A). A does not activate any pyridine C-H bonds, but rather pyridine inserts into a Zr-C bond of A, yielding an azazirconacycle with a dearomatized pyridyl group [Cp2Zr\(2)-N,C-8-(2-c-C3H4)-C5H5N\](2). Kinetic data, isotopelabelling experiments, and DFT calculations indicate that the rate-determining step of this stereospecific reaction is cyclopropane elimination, and that the stability of the intermediate [Cp2Zr((2)-c-C3H4)(NC5H5)](A-py) governs the selectivity of the reaction. Complex2 tautomerizes to [Cp2Zr\(2)-N,C-8-(2-C3H5)-C5H4N\](6) through a base-catalyzed proton migration accompanied by cyclopropyl opening and restoration of conjugation within the zirconacycle.
Published: 2017
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39. Synthesis of Water-Soluble Palladium Nanoparticles Stabilized by Sulfonated N-Heterocyclic Carbenes

Author: Ernesto de Jesús, Yannick Coppel, Simon Tricard, Bruno Chaudret, Juan M. Asensio, Román Andrés, Departamento Química Orgánica y Química Inorgánica, Universidad de Alcalá, Alcalá de Henares, Universidad de Alcalá - University of Alcalá (UAH), 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), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-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), 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-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 de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: organometallic chemistry, 010405 organic chemistry, Organic Chemistry, Thermal decomposition, Inorganic chemistry, chemistry.chemical_element, Nanoparticle, General Chemistry, palladium, 010402 general chemistry, 01 natural sciences, Decomposition, Catalysis, 0104 chemical sciences, Styrene, n-heterocyclic carbene ligands, chemistry.chemical_compound, chemistry, nanoparticles, [CHIM.COOR]Chemical Sciences/Coordination chemistry, aqueous phase, Carbene, Organometallic chemistry, Palladium
Abstract: International audience; A strategy involving the decomposition of palladium(II) organometallic complexes with sulfonated N‐heterocyclic carbene ligands leads to the formation of stable and water‐soluble Pd nanoparticles. Three different methodologies (thermal decomposition, reduction under 13CO atmosphere, and reduction with H2) gave particles with different shapes and sizes, ranging from 1.5 to 7 nm. The structures of the organometallic intermediates and organic decomposition products were elucidated by NMR spectroscopy. To check the accessibility of the surface, the nanoparticles were tested as catalysts for the chemoselective hydrogenation of styrene in water. An effect of the particle size on the catalyst activity was observed. The aqueous phase was recycled up to ten times without any precipitation of metallic palladium.
Published: 2017
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40. A Combined 1 H/6 Li NMR DOSY Strategy Finally Uncovers the Structure of Isopropyllithium in THF

Author: Hassan Oulyadi, Ghanem Hamdoun, Catherine Fressigné, Anne Harrison-Marchand, Jacques Maddaluno, Gabriella Barozzino-Consiglio, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Dimer, Organic Chemistry, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Organolithium reagent, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, Monomer, chemistry, Computational chemistry, Reactivity (chemistry)
Abstract: International audience; Despite its common use in synthesis, the structure of isopropylliyhium in THF has never been determined, a dimer being generally proposed but not supported. This paper fills this data gap through a sophisticated NMR study that shows that, in THF at low‐temperature, isopropyllithium is in the form of a 1:2 mixture of a trisolvated monomer and a disolvated dimer in equilibrium. The presence of the monomer, never evoked before, together with a hypo‐solvation of the dimer hinted by DFT calculations, provides a rational explanation to the remarkable reactivity of this organolithium reagent in ethereal solvents.
Published: 2017
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41. Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Author: Kriti Pathak, Thierry Roisnel, Jean-François Halet, Suman Gomosta, Sundargopal Ghosh, Rongala Ramalakshmi, Vincent Dorcet, Koushik Saha, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [Madras, Chennaï], Indian Institute of Technology Madras (IIT Madras), Council of Scientific and Industrial Research (CSIR), University Grants Commission (UGC), IIT Madras, SERB, New Delhi, India [EMR/2015/001274], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Agostic interaction, Inorganic chemistry, chemistry.chemical_element, Carbon–hydrogen bond activation, rhenium, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Structural isomer, [CHIM]Chemical Sciences, 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, sigma boranes, General Chemistry, Rhenium, borates, 0104 chemical sciences, agostic interactions, Octahedron, manganese, Amine gas treating, Phosphine
Abstract: A series of new bis(sigma) borate and agostic complexes of group7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis( benzothiazol-2-yl) amideborate (Na[(H3B)bbza]), trihydro( 2-aminobenzothiazolyl) borate (Na[(H3B)abz]), and dihydrobis( 2-mercaptopyridyl) borate (Na[(H2B)mp(2)]) (bbza= bis(benzothiazol-2-yl) amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn-2(CO)(10)] with Na[(H3B)bbza] formed bis(sigma) borate complex [Mn(CO)(3)(mu H)(2)BHNCSC6H4(NR)] (1; R= NCSC6H4). Octahedral complex [Re(CO)(2)(N3C2S2C12H8)(2)] (2) was generated under similar reaction conditions with [Re-2(CO)(10)]. Similarly, when [Mn-2(CO)(10)] was treated with Na[(H3B)abz], bis(sigma) borate complex [Mn(CO)(3)(mu-H)(2)BH(HN2CSC6H4)] (3) and the agostic complex [Mn(CO)(3)(mu-H)BH(HN2CSC6H4)(2) (4) were formed. To probe the potential formation of agostic complexes of the heavier group7 metals, we carried out the photolysis of [M-2(CO)(10)] with Na[(H2B)mp(2)] and found that [M(CO)(3)(mu-H) BH(C5H4NS)(2)] (5: M= Re; 6: M= Mn) was formed in moderate yield. Complexes 1 and 3 feature a (k(3)-H,H,N) coordination mode, whereas 4, 5, and 6 display both (k(3)-H,N,N) and (k(3)-H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(s) borate complexes [Mn(mu-H)(2)(BHNCSC6H4)(NR)(CO)(2)PL2L'] (R= NCSC6H4; 7a: L= L'= Ph; 7b: L= Ph, L'= Me) and [Mn(mH) 2BHN(NCSC6H4) R(CO)(2)PL2L'] (R= NCSC6H4; 8a: L= L'= Ph; 8b: L= Ph, L'= Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes.
Published: 2017
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42. Asymmetric Sequential Cu‐Catalyzed 1,6/1,4‐Conjugate Additions of Hard Nucleophiles to Cyclic Dienones: Determination of Absolute Configurations and Origins of Enantioselectivity

Author: Jeanne Crassous, Sophie Colombel-Rouen, Thomas Vives, Charlie Blons, Prasad L. Polavarapu, Sean N. Cuskelly, Marie S. T. Morin, Christophe Crévisy, Craig M. Williams, Paul V. Bernhardt, Thibault E. Schmid, Olivier Baslé, Thibault Reynaldo, Hélène Gérard, Marc Mauduit, Stéphanie Halbert, Cody L. Covington, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Vanderbilt University [Nashville], Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Queensland [Brisbane], ANR-12-BS07-0009-01, ANR (10-BLAN-724-1-NCPCHEM), ANR-10-BLAN-0724,NCPCHEM,Non-Conservation de la Parité dans les Systèmes Moléculaires(2010), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Phosphoramidite, configuration determination, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Stereochemistry, Circular Dichroism, Organic Chemistry, Enantioselective synthesis, asymmetric catalysis, conjugate addition, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Nucleophile, Computational chemistry, Vibrational circular dichroism, Optical rotatory dispersion, Bimetallic strip, Copper, Conjugate
Abstract: International audience; The first stereocontrolled Cu-catalyzed sequential 1,6/1,4-asymmetric conjugate addition (ACA) of C-metalated hard nucleophiles to cyclic dienones is reported. The use of DiPPAM (diphenylphosphinoazomethinylate) followed by a phosphoramidite as the stereoinducing ligands facilitated both high ee values for the 1,6-ACA and high de values for the 1,4-ACA reaction components, which thus gave enantioenriched 1,3-dialkylated moieties. The absolute configurations were determined by using vibrational circular dichroism (VCD) and optical rotatory dispersion (ORD) spectroscopy, in combination with DFT calculations and X-ray analysis. Interestingly, DFT calculations for the mechanism of enantioselective 1,6-addition by using an unprecedented Cu-Zn bimetallic catalytic system confirmed this attribution. Lastly, exploring intramolecular cyclization avenues for enantioenriched 1,3-dialkylated products provided access to the challenging drimane skeleton.
Published: 2017
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43. Improved and General Manganese‐Catalyzed N‐Methylation of Aromatic Amines Using Methanol

Author: Anke Spannenberg, Jacob Neumann, Saravanakumar Elangovan, Matthias Beller, Kathrin Junge, Leibniz-Institut für Katalyse (LIKAT Rostock), Leibniz Association-Universität Rostock, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universität Rostock-Leibniz Association, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: borrowing hydrogen, 010405 organic chemistry, amines, Organic Chemistry, Borrowing hydrogen, chemistry.chemical_element, pincer complex, General Chemistry, Manganese, N methylation, 010402 general chemistry, 01 natural sciences, Catalysis, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, Aniline, chemistry, manganese, [CHIM]Chemical Sciences, Organic chemistry, methylation, Methanol
Abstract: International audience; A novel lutidine-based manganese PNP-pincer complex has been synthesized for the selective N-methylation of aromatic amines with methanol. Using borrowing hydrogen methodology, a selection of differently functionalized aniline derivatives is selectively methylated in good yields.
Published: 2017
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44. Borinic Acid Catalysed Reduction of Tertiary Amides with Hydrosilanes: A Mild and Chemoselective Synthesis of Amines

Author: Michaël De Paolis, Tharwat Mohy El Dine, Jérôme Blanchet, Aurélien Chardon, Jacques Rouden, Rémi Legay, Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Reaction mechanism, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Aryl, amines, Organic Chemistry, reduction, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, amides, borinic acid, chemistry.chemical_compound, chemistry, Phenylsilane, Organic chemistry, organocatalysis, Borinic acid, Alkyl
Abstract: International audience; A reduction of various aryl, alkyl, and α,β‐unsaturated amides with phenylsilane, catalysed by a borinic acid, is reported. The unprecedented reaction was carried out under very mild conditions and led to useful amines. Furthermore, the reaction tolerates a variety of functional groups. Initial investigations implicated that an intermediate diarylhydroborane is involved in the reaction mechanism.
Published: 2017
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45. How Do Phosphinates React with Unactivated Alkenes Under Organic Photocatalyzed Conditions? Substrate Scope and Mechanistic Insights

Author: Sami Lakhdar, Fabrice Morlet-Savary, Giovanni Fausti, Annie-Claude Gaumont, Jacques Lalevée, Institut de Science des Matériaux de Mulhouse (IS2M), 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)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)
Subjects: 010405 organic chemistry, Organic Chemistry, Photodissociation, Substrate (chemistry), General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, law.invention, Perchlorate, chemistry.chemical_compound, chemistry, law, Photocatalysis, [CHIM]Chemical Sciences, Electron paramagnetic resonance, Trifluoromethanesulfonate, ComputingMilieux_MISCELLANEOUS
Abstract: The first visible-light-mediated, metal-free hydrophosphinylation of unactivated alkenes with ethyl and butyl phosphinates is described. The reaction works with a low catalyst loading of 9-mesityl-10-methylacridinium perchlorate (Fukuzumi photocatalyst, 0.5 mol %) in the presence of diphenyliodonium triflate as oxidant. The reaction proceeds smoothly and covers a broad scope of substrates. Detailed mechanistic investigations, including EPR spectroscopy, fluorescence and steady-state photolysis, allowed the mechanism of this photoreaction to be rationalized.
Published: 2017
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46. Recent Progress Toward the Synthesis of Trifluoromethyl- and Difluoromethyl-Substituted Cyclopropanes

Author: Maxence Bos, Thomas Poisson, André B. Charette, Philippe Jubault, Xavier Pannecoucke, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Cycloaddition, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, chemistry, Fluorine, [CHIM]Chemical Sciences, Organic chemistry
Abstract: International audience; This Minireview describes recent advances toward the synthesis of trifluoromethyl‐ and difluoromethyl‐substituted cyclopropanes. Synthetic methodologies using [2+1] cycloaddition, ring‐contraction, and ring‐closure cyclopropanations since 2010 are reported.
Published: 2017
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47. Nanocomposites through the Chemistry of Single-Source Precursors: Understanding the Role of Chemistry behind the Design of Monolith-Type Nanostructured Titanium Nitride/Silicon Nitride

Author: Christel Gervais, Mirna Chaker Bechelany, Vanessa Proust, Samuel Bernard, Sylvie Malo, Philippe Miele, Abhijeet Lale, Institut Européen des membranes (IEM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), French Rhone-Alpes council (Cible project) [1897], CEFIPRA agency [5108-1], CNRS, DGA, national research group ``Matinex', French Region Ile de France-SESAME program, Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)
Subjects: Silicon, Thermogravimetric analysis, Processability, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Nitride, 010402 general chemistry, 01 natural sciences, Precursor chemistry, Catalysis, chemistry.chemical_compound, symbols.namesake, Titanium, Nanocomposite, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Titanium nitride, Nanostructures, 0104 chemical sciences, Amorphous solid, Silicon nitride, chemistry, Chemical engineering, symbols, 0210 nano-technology, Tin, Raman spectroscopy
Abstract: International audience; Monolith-type titanium nitride/silicon nitride nanocomposites, denoted as TiN/Si3N4, have been prepared by a reaction of polysilazanes with a titanium amide precursor, warm pressing of the resultant polytitanosilazanes, and subsequent pyrolysis of the green bodies at 1400 degrees C. Initially, a series of polytitanosilazanes was synthesized and the role of the chemistry behind their synthesis was studied in detail by using solid-state NMR spectroscopy, elemental analysis, and molecular-weight measurements. The intimate relationship between the chemistry and the processability of these precursors is discussed. Polytitanosilazanes display the appropriate requirements for facile processing in solution and as a melt, but they must be treated with liquid ammonia to be adapted for solid-state processing, that is, warm-pressing, to design dense and mechanically stable structures after pyrolysis. We provide a comprehensive mechanistic study of the nanocomposite conversion based on solid-state NMR spectroscopy coupled with thermogravimetric experiments. HRTEM images coupled with XRD and Raman spectroscopy confirmed the unique nanostructural features of the nanocomposites, which appear to be a result of the molecular origin of the materials. The as-obtained samples are composed of an amorphous Si3N4 matrix, in which TiN nanocrystals are homogeneously formed in situ in the matrix during the process. The hardness and Young moduli were measured and are discussed.
Published: 2016
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48. Fluorogenic Behaviour of the Hetero-Diels-Alder Ligation of 5-Alkoxyoxazoles with Maleimides and their Applications

Author: Cyrille Sabot, Kévin Renault, Antoine Lizzul-Jurse, Laurie-Anne Jouanno, Pierre-Yves Renard, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and University of Ottawa [Ottawa]
Subjects: 010405 organic chemistry, Organic Chemistry, Chemical biology, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Diels alder, Peptide chemistry, [CHIM]Chemical Sciences, Bioorthogonal chemistry, Maleimide, Oxazole
Abstract: International audience; Fluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero‐Diels–Alder reaction of 5‐alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions.
Published: 2016
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49. 9H-Quinolino[3,2,1-k]phenothiazine: A New Electron-Rich Fragment for Organic Electronics

Author: Denis Tondelier, Cassandre Quinton, Urelle Biapo, Bernard Geffroy, Joëlle Rault-Berthelot, Cyril Poriel, Olivier Jeannin, Sébastien Thiery, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique des interfaces et des couches minces [Palaiseau] (LPICM), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), We thank the CDIFX and CRMPO (Rennes), GENCI (France) and CINES (Montpellier, c2016085032), the ISN (Gif Sur Yvette) and the ANR (n°11-BS07-020-01 and 14-CE05-0024) for financial support and for a studentship (S.T.)., ANR-14-CE05-0024,Men in blue,Ingénierie moléculaire de l'état triplet de semi-conducteurs organiques bipolaires : Vers de nouveaux designs moléculaires(2014), ANR-11-BS07-0020,HOME-OLED,Design de Matériaux hôtes pour des Diodes Organiques Electrophosphorescentes bleues haute performance : une nouvelle approche(2011), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: spiro compounds, Stereochemistry, Context (language use), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, symbols.namesake, OLED, organic semiconductors, HOMO/LUMO, Organic electronics, Chemistry, Carbazole, Organic Chemistry, Fermi level, quinolinophenothiazine, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, organic light-emitting diodes, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Organic semiconductor, Crystallography, symbols, 0210 nano-technology, Phosphorescence
Abstract: International audience; A new electron-rich fragment, namely the qui-nolinophenothiazine (QPTZ) is reported. TheQ PTZ fragment incorporated in spiroconfigured materials leads to higher performance in blue Phosphorescent OLEDs than structurally related phenylacridine and indoloacridine based materials (increasing the HOMO energy level,m od-ulating the spin-orbit coupling, etc.) and leads to highly efficient blue phosphorescent organic light emitting diodes, indicatingt he strongp otential of this new molecular fragment in organic electronics. Over the last 30 years,t he fantastic emergence of organic electronics is assignable to the design,t he synthesis and the study of thousands of organic semiconductors (OSCs) with specific properties fitting with the different electronic devices. [1–4] Since the discoveryo ft he " host/guest concept " in phosphorescent organic light-emitting diodes (PhOLEDs), [5] the designo fO SCs usable as host materials for blue-emitting phosphors has been an intense research field worldwide. [4] In addition to its high thermal/morphological stabilitya nd its high triplet energy (E T), an ideal host should also possess ab ipolar character,w ith HOMO and LUMO energy levels adapted to the Fermi levels of the electrodes. [6–9] However,t here is ac ertaina ntinomy between ah igh E T (essential to insure efficient energy transfers) and as hort HOMO/LUMO gap (essential to insure efficient charge injection) and the best trade-off should be found for the ideal host. If the nature of the linkage [10] between the electron rich and the electron-poor units is of key importance to control the E T as well as the HOMO/LUMO gap, their intrinsic properties remainn everthelesst he most important characteristics. In this context, the widely known electron-rich carbazole fragment has led to impressive breakthroughs and is nowadays an important buildingb lock in organic electronics. [11, 12] Around the molecular structure of carbazole, many other car-bazole-like fragments have been developed in the recent years sometimes surpassing the performance of the carbazole fragment in electronics. Thus, indolocarbazole (IC), [13] phenylacri-dine (PA) [14–16] and more recentlyi ndoloacridine (IA) [17] are nowadays key building blocks, widely used in all organic electronic devices (Scheme 1). As the future of organic electronics strongly relies on the discoveryo fn ovel elementarym olecular fragments, such as the new bithiophenesulfonamide building block recently reported by Marks,F acchettie ta l., [19] we wish to report herein an ew promising electron-rich core, namely the quinolinophe-Scheme1.Phenylacridine (PA, left), [14, 18] indoloacridine(IA, middle) [17] and quinolinophenothiazine (QPTZ,r ight) based semiconductors.
Published: 2016
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50. Recent Advances in the Synthesis of SCF2H- and SCF2FG-Containing Molecules

Author: Xavier Pannecoucke, Heng-Ying Xiong, Tatiana Besset, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Nanotechnology, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Molecule, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract: International audience; In recent years, much interest has been paid to difluoromethylthiolated molecules as the “SCF2” moiety is a key motif in drug and agrochemical research. Consequently, the development of versatile strategies for the selective synthesis of SCF2H- and SCF2FG-containing molecules (FG= functional group) has attracted a lot of attention and inspired the scientific community to design new tools. This Minireview highlights the major progress made in this field. Particularly, methodologies developed for the difluoromethylation of sulfur-containing molecules and the direct construction of CSCF2 bonds in various classes of compounds are showcased and discussed.
Published: 2016
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