Article
Chemistry, Multidisciplinary
Lu Wang, Minxu Shi, Xiaoping Chen, Nicholas Su, Weili Luo, Xiaheng Zhang
Summary: In this study, aromatic N-heterocyclic radicals were generated and utilized for the functionalization of unactivated alkenes, leading to the efficient synthesis of alkylated N-heterocyclic amines with medicinal relevance. This approach offers a novel retrosynthetic disconnection for the synthesis of therapeutic molecules and can be extended to the synthesis of densely functionalized heterocyclic amines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yuting Qiu, Haiyan Yuan, Xiaoying Zhang, Jingping Zhang
Summary: Computational studies of CPA-catalyzed DyKAH reactions reveal a catalytic asymmetric model involving pi-allylic carbocationic intermediates, with high E/Z selectivity achieved through intermolecular proton transfer. Noncovalent interactions within the electrostatic environment created by the phosphoric acid are key to explaining the enantioselectivity, while the chiral SPINOL scaffolds control the signs of enantioselectivity through substrate binding pocket configurations. Overall, understanding these mechanisms is crucial for guiding DyKAH reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Akshi Tyagi, Sunita Mondal, Anmol, Vikas Tiwari, Tarak Karmakar, Subrata Kundu
Summary: The research demonstrates that the hydroamination of electron-deficient olefins can be efficiently carried out using the (CAAC)Cu-Cl catalyst at room temperature and under an open atmosphere, and the catalyst also shows excellent efficiency in the hydroaryloxylation and hydroalkoxylation of alkenes. Detailed computational studies reveal that the reaction proceeds via either a four-membered or a six-membered cyclic transition state containing the copper ion.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Mandapati Bhargava Reddy, Sakthivel Prabhu, Ramasamy Anandhan
Summary: An unprecedented reductive hydroamidative/hydroquinazolinative cascade cyclization of o-alkynylated derivatives was achieved via proton-coupled electron transfer (PCET) under electrolysis. In a single step, the rapid assembly of isoindolinones and novel isoindole-fused quinazolinones were achieved through electrolysis by the hydroamidation of amidyl/quinazolinone aminyl radicals with C-C triple bond addition via 5-exo-dig cyclization followed by olefinic reduction without external reductants. Control and cyclic voltammetry experiments support a mechanistic explanation of the electrochemical cascade, and these experiments indicate that the electrolyte is the source of hydrogen for the olefin reduction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Qing Zhou, Zhi-Wei Yin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: This work describes a chiral aldehyde/palladium catalysis method for asymmetric α-allylation of NH2-unprotected amino acid esters with 1,3-disubstituted allyl acetates. Using different chiral phosphine ligands, both anti- and syn-selective allylation reactions are achieved enantioselectively. A series of α,α-disubstituted amino acid esters with two adjacent chiral centers are produced in moderate-to-excellent yields, diastereoselectivities, and enantioselectivities.
Article
Chemistry, Organic
Zhenwei Wu, Hualing He, Minglei Chen, Linfei Zhu, Weitao Zheng, Yang Cao, Jon C. Antilla
Summary: A new method for the catalytic asymmetric reductive amination of ketones with pinacolborane has been developed, using chiral SPINOL-derived borophosphates as catalysts. Good yields and high enantioselectivities of chiral amine derivatives were achieved under mild reaction conditions. The synthetic applicability of this method has been demonstrated by the asymmetric synthesis of (R)-Fendiline.
Article
Chemistry, Organic
Ryukichi Takagi, Yuichiro Sakai, Duyen Thi Duong
Summary: A binaphthyl derivative with bis(trifluoromethanesulfonimide) (BSI) moiety was developed as a novel Bronsted acid, showing strong acidity in computational prediction. BSI efficiently catalyzed the hydroamination of alkenyl amines and hydroalkoxylation of alkenyl alcohols in HFIP, with adjacent sulfonimide groups playing a crucial role in enhancing acidity.
Article
Chemistry, Organic
Yang Gao, Yushan Cui, Yanping Huo, Jinhong Chen, Minwei She, Xianwei Li, Qian Chen, Xiao-Qiang Hu
Summary: A nickel-catalyzed polarity-reversed hydroamination of olefins has been developed, providing a convenient route to N-alkyl-2-aminobenzophenones intermediates. This method is compatible with a wide range of olefins and anthranils, delivering the desired amines in high yields, making it applicable for organic synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Tim Lippold, Jorg M. Neudoerfl, Axel Griesbeck
Summary: A synthetic route to new heterocyclic 1,1-donor-acceptor-substituted alkenes starting with N-methyl-acridone, xanthone, and thioxanthone was investigated, leading to the formation of products with low yields. The photophysical properties of the compounds were studied using NMR, UV-VIS absorption, and fluorescence spectroscopy, revealing changes in fluorescence and Stokes shift upon protonation of the acridone-derived alkenes.
Article
Polymer Science
Aidan E. Izuagbe, Vinh X. Truong, Bryan T. Tuten, Peter W. Roesky, Christopher Barner-Kowollik
Summary: We introduce a single-chain nanoparticle system that can dynamically adjust its internal structure using visible light. The system consists of linear polymer chains and variable photoresponsive azobenzene units, allowing reversible isomerization. The reversible compaction and isomerization can be observed by changing the light wavelength.
Article
Chemistry, Organic
Yun-Xing Ji, Jinxia Li, Chun-Min Li, Shuanglin Qu, Bo Zhang
Summary: This study presents a visible-light-promoted method for generating amidyl radicals from N-fluorosulfonamides via a manganese-catalyzed N-F bond activation strategy, using a simple manganese complex and a cheap silane as reactants. This method enables the intramolecular/intermolecular hydroaminations of alkenes, two-component carboamination of alkenes, and even three-component carboamination of alkenes, allowing for the preparation of a wide range of valuable aliphatic sulfonamides.
Article
Chemistry, Organic
Ryukichi Takagi, Duyen Thi Duong
Summary: This study used density functional theory calculations to investigate the mechanism of enantioselective intramolecular hydroamination catalyzed by chiral binaphthol N-triflylphosphoramide (NPTA). It reveals the details of the hydrogen bonding mode between NPTA and the substrate, emphasizing the importance of the dual hydrogen binding properties of the thiourea moiety for the reactivity and stereoselectivity of the hydroamination.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Applied
Cong Wang, Tiezheng Jia
Summary: This study presents a mild photocatalytic anti-Markovnikov hydroamination of alkenes to construct N-alkylated sulfoximines with broad substrate tolerance. The method provides a new synthetic strategy for drug discovery and agrochemistry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Fabio Julia, Jiyao Yan, Fritz Paulus, Tobias Ritter
Summary: A vinyl thianthrenium salt has been introduced as an effective vinylating reagent, which can be readily prepared from ethylene gas and is broadly useful in various annulation chemistry reactions. Its unique structural features enable a distinct synthesis and reactivity profile, unprecedented for other vinyl sulfonium derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Lingpu Meng, Jingjie Yang, Mei Duan, You Wang, Shaolin Zhu
Summary: Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed using NiH catalysis with a simple bioxazoline ligand under mild conditions. A variety of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by employing nitroarenes, hydroxylamines and dioxazolones as amination reagents. Chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Marta G. Avello, Stephane Golling, Lai Truong-Phuoc, Loic Vidal, Thierry Romero, Vasiliki Papaefthimiou, Nathalie Gruber, Michael J. Chetcuti, Frederic R. Leroux, Morgan Donnard, Vincent Ritleng, Cuong Pham-Huu, Christophe Michon
Summary: This study demonstrates the successful synthesis of nickel(0) nanoparticles coordinated to NHC ligands bearing N-coordinated cinnamyl moieties. The unique ligand structure prevents aggregation of the nanoparticles into larger inactive species and enables effective and (Z)-selective semi-hydrogenation of alkynes and ynamides.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Edouard Boivin, Sebastien Saitzek, Francois Fauth, Marielle Huve, Pascal Roussel, Houria Kabbour
Summary: In this study, new potential photocatalysts for overall water splitting (OWS) are obtained through kinetically controlled ion exchange reaction from Na2M2O5F2. These photocatalysts contain lone pair containing oxyfluorides and have a pyrochlore structure. The Sn2+ lone pair stereochemical activity and the narrowing of the band gap contribute to their improved photoconduction response.
CHEMISTRY OF MATERIALS
(2023)
Review
Chemistry, Inorganic & Nuclear
Han Peng, Vincent Ritleng, Christophe Michon
Summary: This article reviews the development of supported Noyori-Ikariya catalysts based on ruthenium, rhodium, and iridium for asymmetric transfer hydrogenation and related tandem reactions over the past 7 years. It highlights and discusses the synthesis, reactivity, and recycling of these catalysts.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Physical
Aiman Jrondi, Gaetan Buvat, Francisco De La Pena, Maya Marinova, Marielle Huve, Thierry Brousse, Pascal Roussel, Christophe Lethien
Summary: Vanadium nitride films made by magnetron sputtering method show excellent cycling stability, high rate capability, high surface capacitance values, and little aging of the electrodes. Additionally, new findings about the charge storage mechanism in pseudocapacitive VN films are revealed by nanoscale analysis.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Rafik Benrabaa, Martine Trentesaux, Pascal Roussel, Annick Rubbens, Rose-Noelle Vannier, Axel Lofberg
Summary: NiAlxFe2_xO4 was synthesized and evaluated in methane reforming without pretreatment. The precursor nature significantly influenced the structural, textural, and reactivity properties. The aluminum compound exhibited high catalytic activity, while NiFe2O4 showed poor activity. Powders prepared with chlorides were more active at low temperatures, but this trend diminished at high temperatures. NiAl2O4 from nitrate precursors showed the best catalytic performance.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Chemistry, Applied
Gaspard Hedouin, Racha Abed Ali Abdine, Quentin Dherbassy, Christophe Michon, Ignacio Funes-Ardoiz, Francoise Colobert, Joanna Wencel-Delord
Summary: In this study, we reported the design of original enantiopure dissymmetrical diphosphines, BiaxPhos, bearing two atropisomeric axes. BiaxPhos ligands possess unique chiral architecture and important modularity, making them attractive candidates for asymmetric catalysis. The Ir-BiaxPhos catalyzed asymmetric imines hydrogenation exhibited excellent enantioselectivities and mild reaction conditions. Remarkably, experimental mechanistic investigations and DFT calculations revealed an unexplored mechanistic scenario involving the hydrogenation of the enamine tautomeric form rather than the classic reduction of the imine.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Electrochemistry
Botayna Bounor, Bouchra Asbani, Camille Douard, Dominique Deresmes, Didier Stievenard, Pascal Roussel, Frederic Favier, Christophe Lethien, Thierry Brousse
Summary: To improve the electrochemical performance of 3D micro-supercapacitors, nanostructured MnO2 films need to be conformally deposited onto the 3D template. The growth mechanism of these films obtained through pulsed electrodeposition was studied using in situ Atomic Force Microscopy and Scanning Electron Microscopy to enhance their electrochemical performance. The impact of ON and OFF times during the deposition process was investigated, providing guidelines for tuning the deposit morphology.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ankush Bhatia, Maxime Hallot, Clement Leviel, Pascal Roussel, Jean-Pierre Pereira-Ramos, Christophe Lethien, Rita Baddour-Hadjean
Summary: Investigation of electrochemical lithium (de)intercalation in an atomic layer deposited (ALD) TiO2 anatase thin film on a Si/Al2O3/Pt substrate was performed using Raman spectroscopy. The initial discharge capacity at C/10 rate was 63 mu Ah cm(-2) mu m(-1) (0.5 Li+ mole(-1)), which increased to 77 mu Ah cm(-2) mu m(-1) after further cycles. The ALD thin film exhibited excellent capacity retention over 100 cycles, indicating its good adherence. Raman spectra of LixTiO2 (0 <= x <= 0.5) thin film electrodes suggest the nucleation of the orthorhombic lithiated titanate (LT) Li0.5TiO2 phase at x = 0.1. The LT phase coexisted with tetragonal TiO2 in the composition range of 0.1 <= x <= 0.4, and was pure at x = 0.5. Reversible transformation from orthorhombic LT to tetragonal TiO2 was observed during charging. The high quality of the Raman spectra allowed identification of 12 modes in the 100-800 cm(-1) region for the electrochemically formed LT phase. Raman spectroscopy proved to be a powerful tool for investigating the Li insertion/extraction mechanism in TiO2 thin films.
ADVANCED MATERIALS INTERFACES
(2023)
Review
Chemistry, Multidisciplinary
Khac Huy Dinh, Pascal Roussel, Christophe Lethien
Summary: Microsupercapacitors (MSCs) have not yet reached the industrial level, despite their many advantages, due to the need to optimize electrode material, device configuration, and solid electrolyte in order to improve their performance.
Article
Chemistry, Physical
Yuanyuan Miao, Saifei Yuan, Hao Ren, Ahmed Addad, Alexandre Barras, Pascal Roussel, Mohammed A. Amin, Sabine Szunerits, Rabah Boukherroub
Summary: In this study, an ultrathin hierarchical P-doped MoS2/Ni3S2 heterostructure was synthesized on nickel foam using a one-pot synthesis. The optimized catalyst showed promising activity for hydrogen and oxygen evolution reaction with low overpotentials. Furthermore, the electrode was applied for overall water splitting with low cell voltages and excellent stability. The results highlight the importance of doping and interface engineering in the design of advanced electrocatalytic materials.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Medicinal
Francesca Ruggieri, Philippe Hance, Bruna Gioia, Alexandre Biela, Pascal Roussel, Jean-Louis Hilbert, Nicolas Willand
Summary: This study describes a novel three-step large-scale extraction and purification method for the simultaneous purification of 11,13-dihydrolactucin (DHLc) and lactucin (Lc) from a chicory genotype rich in these sesquiterpene lactones (STLs) and their glucosyl and oxalyl conjugated forms. The results will facilitate the evaluation of the biological potential of chicory-derived STLs and their semisynthetic analogues.
Article
Chemistry, Multidisciplinary
Batoul Almoussawi, Hiroshi Kageyama, Pascal Roussel, Houria Kabbour
Summary: Oxychalcogenides are potential candidates for various applications including energy, and four new compounds in the Ba-V-Q-O system were synthesized and characterized. A novel structure type was found and the selective substitution of selenium was studied to tune the band gap and symmetry.
ACS ORGANIC & INORGANIC AU
(2023)
Article
Chemistry, Multidisciplinary
Miguel Gallardo, Rodrigo Arancibia, Pascal Roussel, Natacha Henry
Summary: This paper describes a convenient synthesis method for obtaining new ferrocene-based sulfonyl diamine derivatives. The compounds [(?(5)-C5H4SO2NH-CH2-CH2-NH2)Fe(?(5)-C5H5)] (1) and [(?(5)-C5H4SO2NH-C6H4-NH2)Fe(?(5)-C5H5)] (2) were prepared by the reaction between (?(5)- C5H4SO2Cl)Fe(?(5)-C5H5) and the respective diamine precursor: ethylenediamine (1) or p-phenylenediamine (2) with good yields (86% for 1; 70% for 2). Both compounds were characterized by various spectroscopic techniques and cyclic voltammetry, and the molecular structure of 1 was determined by single-crystal X-ray diffraction.
JOURNAL OF THE CHILEAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Blandine Fontaine, Youssef Benrkia, Jean-Francois Blach, Christian Mathieu, Pascal Roussel, Ahmad I. Ayesh, Adlane Sayede, Sebastien Saitzek
Summary: Two polymorphic phases (alpha- and beta-Cu2V2O7) of copper pyrovanadate were synthesized and the mechanisms of phase transitions were studied using TGA and DSC. High temperature X-ray diffraction revealed negative thermal expansion coefficients of the lattice parameters. The optimal conditions for producing dense thin films were determined using thermogravimetric analysis and differential scanning calorimetry. The thin films exhibited a beta-Cu2V2O7 polycrystalline phase and showed absorption in the visible range, making them suitable for use as photoanodes.
Article
Chemistry, Multidisciplinary
Preeti, Asif Raza, Amit Anand, Natacha Henry, Arun K. Sharma, Pascal Roussel, Vipan Kumar
Summary: The manuscript describes a highly stereo-/regioselective method for synthesizing a diverse array of substituted-3-hydroxy-2-oxindoles. The synthesized compounds showed anti-proliferative activity against various cell lines, and one compound demonstrated exceptional potency. It inhibited cell proliferation by inducing apoptosis, and molecular docking studies revealed its binding capability to the target protein.
