Article
Chemistry, Multidisciplinary
Liangzhi Pang, Qilin Sun, Zhan Huang, Gen Li, Jiaojiao Liu, Jiaxu Guo, Chuanzhi Yao, Jie Yu, Qiankun Li
Summary: A palladium-catalyzed stereoselective cleavage of the C-P bond has been developed for the synthesis of atropisomers with a P-stereogenic center. The method offers high yields and high stereoselectivity, and the resulting product shows potential as a chiral catalyst in phosphine-catalyzed cycloaddition reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
James E. Baumann, Gojko Lalic
Summary: A new method for the differential dihydrofunctionalization of terminal alkynes has been developed, enabling the synthesis of allylic boronate esters through a reductive three-component coupling reaction. This transformation, promoted by a copper/palladium catalyst system, hydrofunctionalizes both pi-bonds of the alkyne. The method is compatible with a wide range of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Philipp Kohler, Timothe Perrin, Gabriel Schafer
Summary: DABO boronates and nitrobenzenesulfonate esters are crystalline and stable compounds, which can be used for Suzuki-Miyaura cross-coupling reactions.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Dominik Birnthaler, Rok Narobe, Eliseo Lopez-Berguno, Christoph Haag, Burkhard Koenig
Summary: Ligand-to-metal charge transfer (LMCT) photo-catalysis enables the activation and utilization of halides and other heteroatoms in metal complexes. The application of bismuth LMCT in organic radical coupling reactions has been expanded, generating chlorine and carboxyl radicals in net-oxidative and redox-neutral photochemical reactions. The study reveals BiCl4- and BiCl52- as the catalytically active bismuth species under 385 nm irradiation, providing insight into the reactivity of the highly reactive bismuth(II) catalyst fragment through cyclic voltammetry and UV-vis studies.
Article
Chemistry, Multidisciplinary
Nardana Sivendran, Nico Pirkl, Zhiyong Hu, Angelino Doppiu, Lukas J. Goossen
Summary: Halogen-bridged methylnaphthyl (MeNAP) palladium dimers, presented as versatile Pd precursors, demonstrate excellent catalytic performance by in situ conversion into well-defined monoligated complexes. They show benchmark activities in challenging reactions, enable record-setting yields, and can achieve previously elusive cross-couplings.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Chengqiang Cao, Yi Yang, Xin Li, Yunxia Liu, Hui Liu, Zengdian Zhao, Lei Chen
Summary: The reaction, catalyzed by palladium, efficiently constructs two new bonds with high yields, while the alkene group is easily functionalized, leading to the formation of products with a unique structure that is difficult to synthesize.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Guillermo Zaragoza, Lionel Delaude
Summary: The alkylation of caffeine with methyl iodide led to the synthesis of a new compound. Three complexes were obtained through multiple steps and were found to be highly active catalysts for the Suzuki-Miyaura cross-coupling reaction. The reaction showed high yields and could be carried out in a green solvent with low catalyst loading and in the presence of air.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Review
Chemistry, Physical
Dominique Matt, Jack Harrowfield
Summary: Tertiary phosphines and other P(III)-derivatives play a crucial role in homogeneous catalysis, especially compounds with cavity-shaped subunits. This review illustrates the utility of covalently-constructed phosphines that incorporate a cavity and highlights future directions in ligand design.
Article
Biochemistry & Molecular Biology
Aleksandra Blocka, Wojciech Chaladaj
Summary: We report a new method for the synthesis of highly substituted vinylidenecyclopentanes with good yields, complete selectivity, and excellent functional group tolerance. The mechanism involves the oxidative addition of bromoarene to Pd(0), followed by cyclization and reductive elimination. The high regio- and stereoselectivity can be attributed to the 5-exo-dig intramolecular addition of the enol form of the substrate to alkyne activated by the pi-acidic Pd(II) center.
Article
Chemistry, Multidisciplinary
Liyan Fu, Jingwen You, Yasushi Nishihara
Summary: This method utilizes a palladium catalyst to synthesize unsymmetrical biaryls by cross-coupling acyl chlorides with potassium perfluorobenzoates under redox-neutral conditions. Compared to traditional methods, this synthetic strategy allows for the easy preparation of reactants from inexpensive aromatic carboxylic acids.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Miquel Navarro, Markus Holzapfel, Jesus Campos
Summary: A cavity-shaped gold(I) complex derived from a bulky tri-(ortho-biaryl)-phosphine ligand exhibits preferred selectivity towards terminal functionalities in the gold(I)-catalysed hydration of alkynes under mild heating, thanks to a well-defined pocket as the catalytic active site. This selectivity differs from other gold(I) complexes with bulky phosphine ligands, which show reduced selectivity or similar behavior towards both internal and terminal alkynes. We also explore the potential of gold(III) derivatives for the same catalytic process.
Review
Chemistry, Inorganic & Nuclear
Jose-Antonio Garcia-Lopez, Isabel Saura-Llamas
Summary: This manuscript reviews different approaches for the synthesis of C,C-palladacycles and their relevance in catalytic transformations. The strategies include elemental steps like oxidative addition of C-C bonds and more complex processes involving multiple Pd chemistry steps. Furthermore, it highlights synthetic methodologies based on Pd catalysis with C,C-palladacyclic intermediates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Hayato Fujimoto, Kosuke Yasu, Mamoru Tobisu
Summary: This report discusses recent studies on catalytic transformations involving a non-classical mode of molecular activation by tertiary phosphines and N-heterocyclic carbenes (NHCs). The results show that by designing specific catalytic protocols, synthetic transformations that are otherwise unattainable can be achieved, including intermolecular carbofluorination of alkynes and hydroalkenylation of enol ethers. The use of imidazolium-based NHCs was explored for nucleophilic aromatic substitution reactions as well as nucleophilic activation of styrene derivatives, generating non-stabilized vinyl anion equivalents.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Review
Chemistry, Multidisciplinary
Catriona C. James, Bas de Bruin, Joost N. H. Reek
Summary: The importance of transition metal catalysis lies in its wide range of applications, including the synthesis of chemicals, natural products, and pharmaceuticals. However, a relatively new application is the catalysis of new-to-nature reactions inside living cells. The complex environment of living cells poses challenges to transition metal catalysts due to the potential inhibition or deactivation by various biological components. In this review, we summarize the current progress in the field of transition metal catalysis, focusing on the evaluation of catalysis efficiency under living cell and biological conditions. Catalyst poisoning is a common issue in this field, and we suggest that future research should explore physical and kinetic protection strategies to enhance the reactivity of catalysts in cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)