Article
Chemistry, Multidisciplinary
Chao Xu, Hao Zhang, Shouang Lan, Jinggong Liu, Shuang Yang, Qi Zhang, Xinqiang Fang
Summary: Transition-metal-catalysed reactions of cyclic ethynylethylene carbonates have been extensively investigated due to their robustness in forming new bonds and constructing diverse molecules. A novel reaction pattern is reported, where cyclic ethynylethylene carbonates firstly undergo rearrangement to release allenal intermediates, which then react with various nucleophiles to produce synthetically useful allylic and propargylic allenols, phosphorus ylides, and cyclopropylidene ketones through an addition process rather than substitution pathway. The products allow for further transformations, and mechanistic studies reveal that the reaction proceeds via base-mediated deprotonation as the key step to induce the rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Thangaiyan Pooventhiran, Nripen Khilari, Debasis Koley
Summary: The CuII-catalyzed Chan-Lam reaction is an important synthetic method for constructing C-O bonds through oxidative coupling of arylboronic esters with heteroatom nucleophiles. Although this reaction has been experimentally explored, the mechanistic understanding is still limited. In this study, computational investigations were conducted to unravel the key steps and energetic changes in the reaction mechanism, providing valuable information for further optimization and application of this reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jia-Le Xie, Zheng Xu, Han-Qi Zhou, Yi-Xue Nie, Jian Cao, Guan-Wu Yin, Jean-Philippe Bouillon, Li-Wen Xu
Summary: The study presents a highly enantioselective hydrosilylation of ynones using a palladium catalyst with a chiral ligand, leading to the formation of a series of silicon-stereogenic silylenones with high yield and enantioselectivity. The reaction mechanism and origin of high degree of stereoselectivity were elucidated through density functional theory calculations, highlighting the importance of aromatic interactions in the reaction.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yelu Shi, Gianna Stella, Jia-Min Chu, Yong Zhang
Summary: This study reveals the importance of HNO binding and a proton-coupled electron transfer mechanism for HNO reaction through quantum chemical research on Cu cyclams. The results indicate that steric effect is the primary factor, and electronic factor is the secondary factor, but the combined effects can lead to unexpected reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Neha Antil, Naved Akhtar, Rajashree Newar, Wahida Begum, Ajay Kumar, Manav Chauhan, Kuntal Manna
Summary: The development of efficient and enantioselective heterogeneous catalysts based on abundant elements and inexpensive ligands is crucial for environmentally friendly and cost-effective production of optically active compounds. This study demonstrates the synthesis of chiral amino alcohol-functionalized metal-organic frameworks as highly enantioselective base-metal catalysts for asymmetric organic transformations.
Article
Chemistry, Physical
Jingzhao Xia, Takahiro Hirai, Shoichiro Katayama, Haruki Nagae, Wanbin Zhang, Kazushi Mashima
Summary: This study presents a comprehensive investigation of the reaction mechanism for a coupling reaction catalyzed by a Ni/Cu cooperative catalyst system, providing direct access to valuable stereocenters with high enantio- and diastereoselectivity. The mechanism of the bimetallic cooperative catalyst system was elucidated through isolation and characterization of key complexes, deuterium labeling experiments, kinetic studies, and density functional theory calculations. The turnover-limiting step involves a proton-transfer step between Ni and Cu complexes to yield the desired products with specific stereochemistry.
Article
Chemistry, Multidisciplinary
Cai-Yun Ding, Man Li, Rong-Zhen Liao
Summary: Density functional theory calculations were used to investigate the synergistic effect of Pd(0) and Cu(I) catalysis on the selective formation of allylated indole. The addition of Cu(I) catalyst significantly decreased the energy barrier for the intramolecular cyclization, leading to the formation of indole. The mechanistic insights provided a better understanding of the factors governing selectivity in synergistic Pd/Cu catalysis.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhi-Zhou Pan, Jia-Heng Li, Hu Tian, Liang Yin
Summary: A copper(I)-catalyzed asymmetric allylation of ketones with 2-aza-1,4-dienes has been demonstrated, providing a series of functionalized homoallyl tertiary alcohols with high to excellent enantioselectivity. The deprotonation of N-allyl-1,1-diphenylmethanimines is the rate-determining step in the reaction, generating nucleophilic allyl copper(I) species. The utility of this method has been demonstrated by the asymmetric synthesis of (R)-boivinianin A and (R)-gossonorol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Roel L. M. Bienenmann, Alexandra J. Schanz, Pascale L. Ooms, Martin Lutz, Daniel L. J. Broere
Summary: In this study, the first structurally characterized anionic dicopper hydride complex was described. The complex displayed distinct reactivity compared to low-nuclearity copper hydrides, resembling that of copper hydride clusters. This difference in reactivity was attributed to the tightly bound dinuclear core within the dinucleating ligand scaffold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Abing Duan, Fengjiao Xiao, Yu Lan, Linbin Niu
Summary: This review summarizes the representative advancements in theoretical studies on transition-metal-catalyzed reductive coupling reactions, focusing on the mechanisms of key steps and the activation modes of electrophiles, as well as the generation of selectivity. The mechanism of the reduction of high-oxidation-state catalysts and the construction of new chemical bonds are also discussed.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Organic
Ying Wang, Zi-Lu Wang, Wei-Wei Ma, Yun-He Xu
Summary: A copper-catalyzed regioselective Markovnikov 3,4-hydrosilylation of 2-substituted 1,3-dienes has been successfully achieved. A wide range of 2-substituted 1,3-dienes and trihydrosilanes are compatible under the optimal conditions. The use of a bisphosphine ligand with a rigid backbone provides the Markovnikov 3,4-hydrosilylation product with better yield and selectivity. Additionally, the synthetic utilities of the allylsilanes were demonstrated through their flexible derivatizations.
Article
Chemistry, Physical
Srimanta Manna, Joannes Peters, Aitor Bermejo-Loïpez, Fahmi Himo, Jan-E. Backvall
Summary: The mechanism of dehydrogenation of amines catalyzed by (cyclopentadienone)iron carbonyl complexes was studied using KIE measurements, intermediate isolation, and density functional theory calculations. The intermediates of (cyclopentadienone)iron-amine were isolated and characterized, and the KIEs observed supported a stepwise dehydrogenation process. Density functional calculations confirmed a stepwise mechanism involving hydride transfer and proton transfer steps.
Article
Chemistry, Organic
Kurt Puntener, Raphael Bigler, Kenta Stier, Marek P. Checinski
Summary: This study investigates the asymmetric hydrogenation of beta-ketoesters catalyzed by [RuCl2(MeOH)(2)((R)-MeOBIPHEP)]. It is found that HCl acts as both an activator and has a significant impact on the reaction. The study also explains the effects of common phosphorus substituents on the activity of the catalyst.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Guanghao Huang, Regis Guillot, Cyrille Kouklovsky, Boris Maryasin, Aurelien de la Torre
Summary: A broadly applicable diastereo- and enantioselective inverse-electron-demand Diels-Alder reaction of 2-pyrones and acyclic enol ethers is reported, leading to the synthesis of bridged bicyclic lactones with high yields and enantioselectivities using a copper(II)-BOX catalytic system. Mechanistic studies suggest a stepwise mechanism, and the synthetic potential of the bridged bicyclic lactones is demonstrated through the enantioselective synthesis of polyfunctional cyclohexenes and cyclohexadienes, as well as a carbasugar unit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Yannick Geiger, Stephane Bellemin-Laponnaz
Summary: Non-linear effects between enantiomeric excesses of ligand and product are common in asymmetric catalysis, and they are useful tools for mechanistic investigations. This study shows that catalyst precipitation affects the shape and amplitude of non-linear effects curves, and it also observes several peculiar features. Overall, this research provides a better understanding of chiral catalytic systems.
Article
Chemistry, Physical
Anna Bonfiglio, Pei-Wan Hsiao, Yin Chen, Christophe Gourlaouen, Quentin Marchand, Vincent Cesar, Stephane Bellemin-Laponnaz, Yun-Xin Wang, Chin-Wei Lu, Chantal Daniel, Federico Polo, Hai-Ching Su, Matteo Mauro
Summary: This study presents a class of bright heterobimetallic emitters with enhanced fluorescence efficiency and radiative rate constant. The application of these bimetallic complexes in light-emitting electrochemical cells achieves high external quantum efficiency.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Refka Guermazi, David Specklin, Christophe Gourlaouen, Pierre Fremont, Samuel Dagorne
Summary: This study reports on the synthesis, structure, and use of new [(IPrCl)Zn-R](+) and [((IBu)-Bu-t)Zn-R](+) cations in alkyne hydroboration catalysis. The results show that [(IPrCl)Zn-C6F5](+) cation exhibits the highest catalytic activity.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Julien Egly, Weighang Chen, Aline Maisse-Francois, Stephane Bellemin-Laponnaz, Thierry Achard
Summary: Amide synthesis is a crucial transformation in chemistry and biology. N-heterocyclic carbene-based ruthenium catalyst systems have been proven to be active for direct synthesis of amides. In this study, a series of Ru complexes with thioether-functionalized N-heterocyclic carbene ligands were prepared and applied to the amidation reaction, resulting in high conversions but moderate yields.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Damien Bissessar, Julien Egly, Thierry Achard, Pascal Steffanut, Matteo Mauro, Stephane Bellemin-Laponnaz
Summary: A tetranuclear copper-iodide cluster has been identified as a stable precursor for further post-functionalization, allowing the direct functionalization of alkenes and providing access to a wide range of luminescent copper cubane complexes, including the first example of water-soluble luminescent cubane copper iodide.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Thibault Thierry, Yannick Geiger, Stephane Bellemin-Laponnaz
Summary: Phenomena related to asymmetric amplification are crucial for understanding the emergence of homochirality in life. This study focuses on asymmetric catalysis and investigates non-linear effects in chiral amplification. The authors provide experimental evidence of a new nonlinear hyperpositive effect in enantioselective zinc-catalyzed alkylation. Their research also reveals a mechanism involving both monomeric and dimeric complexes that contribute to different enantioselectivities.
Article
Chemistry, Physical
Yuri C. A. Sokolovicz, Antonio Buonerba, Carmine Capacchione, Samuel Dagorne, Alfonso Grassi
Summary: The zinc complex demonstrates high catalytic activity and selectivity in the polymerization of cyclohexene oxide (CHO), producing poly(cyclohexene oxide) (PCHO) with remarkable TOF values at room temperature. The complex also catalyzes the ring-opening copolymerization of CO2 with CHO, yielding poly(cyclohexene carbonate) (PCHC) with high polydispersity index values. The formation of dinuclear species during the reaction highlights potential new zinc catalysts that impact the polymerization process.
Article
Oncology
Conor McCartin, Candice Dussouillez, Chloe Bernhard, Eric Mathieu, Juliette Blumberger, Monique Dontenwill, Christel Herold-Mende, Ahmed Idbaih, Philippe Lavalle, Stephane Bellemin-Laponnaz, Antoine Kichler, Sylvie Fournel
Summary: The resistance and recurrence of tumors pose major challenges for cancer patient survival. Research has identified a subset of stem-cell-like cells in tumors that contribute to this problem. Developing new chemotherapeutic compounds to target these cells is of great interest for more effective cancer treatments.
Article
Engineering, Biomedical
Conor McCartin, Juliette Blumberger, Candice Dussouillez, Patricia Fernandez de Larrinoa, Monique Dontenwill, Christel Herold-Mende, Philippe Lavalle, Beatrice Heurtault, Stephane Bellemin-Laponnaz, Sylvie Fournel, Antoine Kichler
Summary: Cationic polymers like polyethylenimine (PEI) have been widely used as gene delivery agents and drug delivery agents. Recent studies have shown that certain polycations have higher toxicity towards cancer stem cells (CSCs) than differentiated tumor cells. Since CSCs play a critical role in cancer drug resistance, tumor recurrence, and poor clinical prognosis, it is important to investigate compounds that can target and eliminate these cells.
JOURNAL OF FUNCTIONAL BIOMATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Salvatore Impemba, Irene Tozio, Giuseppina Roviello, Samir Mameri, Samuel Dagorne, Stefano Milione
Summary: Mono- and bimetallic aluminum complexes with bidentate NS or tetradentate NSSN ligands were synthesized and characterized. The aluminum centers in these complexes have tetrahedral coordination geometries surrounded by anionic nitrogen and neutral sulfur atoms. X-ray diffraction studies confirmed the structure of the complexes with thioethyl or thiopropyl bridge. Both mono- and bimetallic aluminum complexes showed fluxional behaviors in solution. The bimetallic complex with the shortest bridge (ethyl bridge) exhibited the highest activity in the ring opening polymerization of L-lactide.
Article
Chemistry, Physical
Jordi Vila, Miquel Sola, Thierry Achard, Stephane Bellemin-Laponnaz, Anna Pla-Quintana, Anna Roglans
Summary: This article describes the [2 + 2 + 2] cycloaddition of 1,5-bisallenes and alkynes under the catalysis of Rh(I) with hemilabile thioether-functionalized N-heterocyclic carbene ligands. This method effectively provides access to different trans-5,6-fused bicyclic systems with two exocyclic double bonds in the cyclohexene ring. The complete mechanism of this transformation as well as the preference for the trans-fusion over the cis-fusion has been rationalized by density functional theory calculations.
Article
Multidisciplinary Sciences
Damien Bissessar, Thibault Thierry, Julien Egly, Valerio Giuso, Thierry Achard, Pascal Steffanut, Matteo Mauro, Stephane Bellemin-Laponnaz
Summary: We synthesized and studied three new copper halide derivatives 2a-c, which are tetranuclear copper-iodide clusters consisting of a cubane-like {Cu4I4} motif and phosphine ligands P. They differ in the type of phosphines used as ligands: a monophosphine with a single pendant ester unit (2a), two pendant ester units (2b), and a diphosphine containing two esters in the linker (2c). The complexes displayed intense and long-lived photoluminescence in the orange region with PLQY values of 0.43-0.84 at room temperature, mainly associated with a (CC)-C-3 excited state with mixed (XMCT)-X-3 character.
Article
Chemistry, Physical
Gael Printz, Dmytro Ryzhakov, Christophe Gourlaouen, Beatrice Jacques, Samir Messaoudi, Francoise Dumas, Franck Le Bideau, Samuel Dagorne
Summary: We report the first use of thiosquaramides as polymerization catalysts, showing their effectiveness for controlled ring-opening polymerization of lactide in the presence of an alcohol source and NEt3. Comparison with less acidic squaramides reveals the importance of a balanced NH Brönsted acidity for optimal catalytic performance. Surprisingly, DFT-supported calculations demonstrate that secondary interactions between thiosquaramide N-substituents and the incoming lactide are crucial for catalytic activity, which is rarely observed in the field of organo-catalyzed polymerizations. Such findings suggest the significance of catalyst substituent/substrate interactions in various other systems.
Article
Chemistry, Inorganic & Nuclear
Xuejuan Xu, Christophe Gourlaouen, Beatrice Jacques, Samuel Dagorne
Summary: This study reports the synthesis and characterization of novel Zn(II)-based organocations and their application in catalytic reactions. The results demonstrate that these cations exhibit good performance in catalyzing hydrosilylation reactions.
Article
Radiology, Nuclear Medicine & Medical Imaging
T. Thibault, M. Gurung, C. Leuvrey, A. Boos, P. Ronot, I. El Masoudi, P. Hoerner, S. Bellemin-Laponnaz
Summary: This study found that lead-containing gloves may present a risk of metal leaching when in contact with sweat, and the level of lead leaching depends on the acidity of the sweat and the duration of contact. Gloves with a protective lining reduce the transfer of lead into sweat, but significant levels of lead are still present.
