Article
Chemistry, Multidisciplinary
Hao Liang, James P. Morken
Summary: Enantioenriched tertiary alkylboronic esters can be activated by in situ generated adamantyllithium, leading to stereoretentive boron-to-copper transmetalation. The resulting alkylcopper species can react with various electrophiles through cross-coupling reactions, providing synthetically useful compounds with quaternary stereocenters. DFT calculations of the transmetalation process offer insights into reactivity and selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Alexandre Desaintjean, Tobias Haupt, Leonie J. Bole, Neil R. Judge, Eva Hevia, Paul Knochel
Summary: Using the bimetallic combination sBu(2)Mg.2 LiOR (R=2-ethylhexyl) in toluene allows efficient and regioselective Br/Mg exchanges with various dibromo-arenes and -heteroarenes under mild reaction conditions, providing bromo-substituted magnesium reagents. N,N,N ',N '',N ''-pentamethyldiethylenetriamine (PMDTA) finely tunes the regioselectivity of the Br/Mg exchange, and spectroscopic and X-ray crystallographic studies shed light on the mixed Li/Mg constitution of the organometallic intermediates involved in these transformations. These intermediates react effectively with a wide range of electrophiles in good yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Leonie J. Bole, Neil R. Judge, Eva Hevia
Summary: This study describes the activation of sBu(2)Mg towards substituted bromoarenes by adding LiOR (R=2-ethylhexyl), leading to the formation of two different types of organometallic intermediates. NMR spectroscopic studies reveal that the exchange reactions and the formation of intermediates are controlled by a new type of bimetallic Schlenk-type equilibrium.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jairus L. Lamola, Adedapo S. Adeyinka, Frederick P. Malan, Paseka T. Moshapo, Cedric W. Holzapfel, Munaka Christopher Maumela
Summary: The electronic and steric properties of newly developed biaryl phosphacycles were quantified using various experimental and theoretical methods. The study found moderate to good correlations between electronic descriptors derived from P-31-Se-77 coupling constants, C-O stretching frequency, computed bond enthalpies, molecular electrostatic potentials, and the unique steric parameterization studies of phospho-selenides.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Jinran Sun, Lang Huang, Gaojie Xu, Shamu Dong, Chunsheng Wang, Guanglei Cui
Summary: Pre-lithiation is crucial for improving the performance of lithium-ion batteries, including increasing energy density and enhancing initial coulombic efficiency. However, it also affects the cycle life of the batteries. Therefore, finding a balance between high energy density and long cycle life is important.
Article
Chemistry, Inorganic & Nuclear
Nilesh R. Mote, Shahaji R. Gaikwad, Kishor Khopade, Rajesh G. Gonnade, Samir H. Chikkali
Summary: This study reports the synthesis of phosphine-sulfonamide-derived palladium complexes and examines their performance in ethylene oligomerization. A library of 7 palladium complexes were synthesized by varying the donor moiety and their performance in ethylene oligomerization was assessed, with complex C5 showing the best results. The ethylene oligomers produced under optimal conditions had a molecular weight of 1000-1900 g mol(-1), demonstrating the effectiveness of complex C5 in the process.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Tianshi Lv, Xiangzhen Zhu, Zejing Lin, Liumin Suo
Summary: Aqueous Li-ion batteries (ALIBs) are safe, environmentally friendly, and cost-effective, but their advantages in cost and energy density are limited. A new strategy of introducing sacrificial pre-lithiation additives has been proposed to achieve high energy density in ALIBs.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Organic
Stefan Herzog, Alexander Hinz, Frank Breher, Joachim Podlech
Summary: In this study, an air- and moisture-stable helical radical was synthesized and its properties and spectra were determined. The results showed that this radical exhibited good stability, weak triradical character, and significant antiaromaticity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Biochemical Research Methods
Ruijie Yang, Liang Mei, Yingying Fan, Qingyong Zhang, Hong-Gang Liao, Juan Yang, Ju Li, Zhiyuan Zeng
Summary: Understanding complex electrochemical reactions in energy devices has gained global attention. In situ liquid cell transmission electron microscopy allows real-time visualization and analysis of these reactions at the nano scale. This protocol provides detailed procedures for fabricating electrochemical liquid cells and conducting in situ TEM observation of electrochemical reactions. The experimental results demonstrate the potential of this protocol in fabricating high-quality TEM liquid cells and exploring dynamic electrochemical reactions with high resolution.
Article
Chemistry, Physical
Dong Jae Chung, Donghan Youn, Soohwan Kim, Donghyeok Ma, Jiwhan Lee, Won Joon Jeong, Eunjun Park, Joon-Sup Kim, Chulsoon Moon, Ji Yeong Lee, Heeyoung Sun, Hansu Kim
Summary: Research shows that dehydrogenation-driven prelithiation using lithium hydride can significantly improve the initial Coulombic efficiency of silicon monoxide, thereby enhancing the performance of lithium-ion batteries. Silicon monoxide prelithiated through this method exhibits higher capacity and better cycling stability in tests, enabling a significant increase in the energy density of the overall battery system.
Article
Multidisciplinary Sciences
Seok Jeong, Junmo Seong, Sung Wook Moon, Jaewoong Lim, Seung Bin Baek, Seung Kyu Min, Myoung Soo Lah
Summary: The spatial distribution of mixed building blocks in metal-organic frameworks can be modulated by tuning the reaction temperature, leading to the formation of core-shell and uniform microstructures.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Karim Muratov, Fabien Gagosz
Summary: In this research, a new class of structurally simple and easily accessible bulky tri-(ortho-biaryl)phosphine ligands and their gold(I) complexes were synthesized. Their confined nature was demonstrated through X-ray diffraction analysis and comparative evaluation. Despite their notable steric congestion, these complexes exhibited remarkable catalytic activities and unusual selectivities, making them unique in the field of synthetic homogeneous gold catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Nanoscience & Nanotechnology
Chen-Jui Huang, Ya-Ching Hsu, Kassie Nigus Shitaw, Yu-Jhen Siao, She-Huang Wu, Chia-Hsin Wang, Wei-Nien Su, Bing Joe Hwang
Summary: Researchers have extended the lifespan of anode-free lithium metal batteries (AFLMBs) by introducing lithium oxalate as an electrode additive in the cathode. AFLMBs with a composite cathode containing 20% lithium oxalate and LiNi0.3Co0.3Mn0.3O2 exhibited >80% and 40% capacity retention after 50 and 100 cycles, respectively, outperforming AFLMBs using a pure LiNi0.3Co0.3Mn0.3O2 cathode. Surprisingly, the Coulombic efficiency of AFLMBs improved with an increased amount of lithium oxalate in the composite cathode.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Multidisciplinary Sciences
Giichiro Uchida, Kenta Nagai, Yuma Habu, Junki Hayashi, Yumiko Ikebe, Mineo Hiramatsu, Ryota Narishige, Naho Itagaki, Masaharu Shiratani, Yuichi Setsuhara
Summary: In this study, nanostructured Ge and GeSn films were fabricated using He radio-frequency magnetron plasma sputtering deposition. The addition of Sn improved the capacity and cycling performance of lithium-ion batteries with Ge and GeSn anodes.
SCIENTIFIC REPORTS
(2022)
Article
Chemistry, Multidisciplinary
Jairus L. Lamola, Paseka T. Moshapo, Cedric W. Holzapfel, Munaka Christopher Maumela
Summary: A new family of biaryl phosphacyclic ligands have been developed for efficient Suzuki-Miyaura cross-coupling of aryl bromides and chlorides, with successful coupling of sterically hindered and heterocyclic substrates at room temperature.
Article
Chemistry, Organic
Laura Santos, Morgan Donnard, Armen Panossian, Jean-Pierre Vors, Peter Jeschke, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: The N-alkylation of imino-thiazolidinones, which are ambident and weakly nucleophilic, has been achieved through substitution with alkyl fluorosulfonates. These reactive electrophiles are obtained by transforming non-toxic, economic, and commercially available alcohol derivatives with SO2F2 gas. The use of electron-withdrawing groups and DMAc as a solvent allows for a (Z)- and N-endocyclic selectivity in the introduction of various alkyl and polyfluoroalkyl chains.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Pierre Hansjacob, Frederic R. Leroux, Vincent Gandon, Morgan Donnard
Summary: The palladium-catalyzed silylcyanation of ynamides is highly selective, producing exclusively tetrasubstituted 2-aminoacrylonitriles derivatives. The stereoselectivity is directly controlled by the nature of the substituent at the beta-position of the ynamide. The reaction is tolerant of various functional groups and provides a general method to access fully substituted 2-aminoacrylonitriles. The mechanism of this intriguing transformation is elucidated by computational study, and the range of 2-aminoacrylonitriles is expanded through postfunctionalization using the newly installed vinylsilane functionality.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Clemence Bonnefoy, Emmanuel Chefdeville, Christian Tourvieille, Armen Panossian, Gilles Hanquet, Frederic Leroux, Fabien Toulgoat, Thierry Billard
Summary: This paper presents a study on the properties and potential applications of carbamoyl fluoride, including stability, lipophilicity, and synthesis methods. The results demonstrate its potential use in radiochemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jordan Berreur, Alberto Diez-Varga, Augustin Manel, Frederic R. Leroux, Armen Panossian
Summary: The direct oxidative monofluorination of sulfoxides can be achieved using a strongly oxidizing, powerful electrophilic fluorination reagent [FXe][OTf], without the need for a chloride promoter. This method allows the synthesis of highly desirable strongly Lewis acidic fluorosulfoxonium cations, which were previously difficult to access using the XeF2/NEt4Cl system. Experimental and theoretical studies were conducted to evaluate the Lewis acidities of the prepared sulfur(VI) cations, and early insights into the mechanism of these fluorination reactions were obtained through preliminary studies with chiral sulfoxides.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
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, Organic
Stephane Golling, Pierre Hansjacob, Nassim Bami, Frederic R. Leroux, Morgan Donnard
Summary: This paper reports a palladium-catalyzed annulation reaction that can synthesize polysubstituted amino-indenones, with different regioselectivity observed between different ynamides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Florian Audet, Morgan Donnard, Armen Panossian, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: Sulfuryl fluoride is a gas used as a fumigant, but it has also gained interest in organic synthesis due to its unique properties. It has been used for sulfur-fluoride exchange chemistry and as an efficient activator in classic organic synthesis, forming fluorosulfonates. Recent research has focused on metal-catalyzed transformations from aryl fluorosulfonates and nucleophilic substitution reactions on polyfluoroalkyl alcohols, highlighting the advantages of polyfluoroalkyl fluorosulfonates compared to alternative reagents.
Article
Chemistry, Multidisciplinary
Clemence Bonnefoy, Armen Panossian, Gilles Hanquet, Frederic R. Leroux, Fabien Toulgoat, Thierry Billard
Summary: In this study, 2,4-dinitro-trifluoromethoxybenzene (DNTFB) was used as a trifluoromethoxylating reagent to perform nucleophilic substitution reactions under mild metal-free conditions. The reactions involved substrates with different leaving groups, including direct dehydroxytrifluoromethoxylation. A mechanistic study rationalized the reactions and proposed only three reaction conditions based on the reactivity of the starting substrates.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Laura Santos, Florian Audet, Morgan Donnard, Armen Panossian, Jean-Pierre Vors, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: An efficient method for the synthesis of high-value N-polyfluoroalkyl anilines, primary polyfluoroalkylamines, and N,N-bis(polyfluoroalkyl) amines via N-polyfluoroalkylation of sulfonamides and phthalimide derivatives using sulfuryl fluoride (SO2F2) is reported. The in situ formation of polyfluoroalkyl fluorosulfonates from commercially available fluorinated alcohols and economical sulfuryl fluoride is advantageous in terms of environmental impact and cost. This general method allows for the polyfluoroalkylation of a variety of substrates, providing valuable building blocks for life science applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Clotilde Placais, Sherif J. Kaldas, Morgan Donnard, Armen Panossian, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: This work presents the synthesis of aryl and alkenyl halides from fluorosulfonates using commercially available ruthenium catalysts. It is the first study to efficiently convert phenols to aryl halides with chloride, bromide, and iodide. Fluorosulfonates can be easily prepared using sulfuryl fluoride (SO2F2) and cost-effective substitutes for triflates. Additionally, this work also reports an efficient coupling of alkenyl fluorosulfonates for the first time. Representative examples demonstrate that the reaction can be carried out in a one-pot process, starting directly from phenol or aldehyde.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Marie-Charlotte Belhomme, Thomas Guerin, Armen Panossian, Frederic R. Leroux
Summary: The reaction of diphenylphosphine oxide with two aryne precursors was studied to obtain functionalizable nonsymmetrical dibenzophospholes. The reactions were found to be influenced by substituents on the aryne precursors that can coordinate with the incoming lithiated nucleophile.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2023)
Article
Chemistry, Organic
Anais Loison, Gilles Hanquet, Fabien Toulgoat, Thierry Billard, Armen Panossian, Frederic R. Leroux
Summary: This paper reports an unprecedented synthesis of difluoromethoxylated nitrogen-containing heterocycles from α-(difluoromethoxy)ketones as versatile building blocks. Pyrazoles, isoxazoles, and pyrimidines were obtained via an enaminone intermediate, and a Fischer indole synthesis was achieved in the direct reaction of α-(difluoromethoxy)ketones with arylhydrazines. These uncommon or even novel scaffolds, with the directly attached emerging fluorinated group (OCF2H), have high potential in life sciences and provide an interesting alternative to classical fluorinated groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Anthony J. Fernandes, Bastien Michelet, Armen Panossian, Agnes Martin-Mingot, Frederic R. Leroux, Sebastien Thibaudeau
Summary: Understanding the impact of emerging fluorinated motifs is crucial due to the increasing use of fluorine in various fields. This study demonstrates the significant effect of a local partial charge inversion through the replacement of a CHCH3 group with a CFCF3 group. This strategy enables the diastereoselective reduction of 5-membered ring oxocarbenium ions, leading to the formation of highly substituted tetrahydrofurans.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Pierre Hansjacob, Celia Schwoerer, Frederic R. Leroux, Morgan Donnard
Summary: Here we report the efficient and selective two-step synthesis of various 3-silyl-2-amidoindenones from easily accessible ynamides. This synthesis involves a regio- and stereo-selective silylcyanation followed by a Houben-Hoesch type cyclization. By utilizing post-transformations, a range of 3-substituted 2-amidoindenones could be obtained. This method offers a simple and selective approach to synthesize polyfunctionalized 2-amidoindenones, with the notable achievement of true structural diversity at position 3.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Meeting Abstract
Radiology, Nuclear Medicine & Medical Imaging
Clemence Bonnefoy, Emmanuel Chefdeville, Christian Tourvieille, Armen Panossian, Gille Hanquet, Frederic Leroux, Fabien Toulgoat, Thierry Billard
NUCLEAR MEDICINE AND BIOLOGY
(2022)
