Article
Chemistry, Physical
Murat Kaloglu, Ismail Ozdemir
Summary: Six novel palladium N-heterocyclic carbene complexes with different ancillary ligands were successfully prepared and used as pre-catalysts in the Buchwald-Hartwig amination reaction. These complexes showed good catalytic activity in the amination of cyclic secondary amines with aryl chlorides, leading to moderate to high yields of N-arylamines under mild reaction conditions.
Article
Chemistry, Medicinal
Kohei Motojima, Abhijit Sen, Yoichi M. A. Yamada, Hiromasa Kaneko
Summary: Catalyst design using machine learning is important for reducing costs and development time in various industrial fields. This study focused on a reaction system involving Buchwald-Hartwig type cross-coupling (BHCC) and Suzuki-Miyaura type cross-coupling (SMCC) reactions. By constructing a machine-learning model considering all experimental conditions, the study aimed to accurately predict product yield for both BHCC and SMCC reactions and design catalysts that achieve target yield and develop novel reactions. Bayesian optimization was used with established variables to design new catalysts and improve reaction selectivity. Additionally, the catalyst design successfully introduced new reactions involving Cu, Rh, and Pt catalysts in a reaction system that previously only reacted with Ni or Pd transition metals.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhi-Mao Zhang, Yu-Ting Xu, Li-Xiong Shao
Summary: Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand were successfully synthesized in moderate to good yields. One of the complexes showed efficient catalytic activity in the Buchwald-Hartwig amination reaction, providing an alternative catalyst for the coupling of challenging yet cost-low aryl chlorides.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Lin Feng, Jiaxin Yao, Lin Yu, Wengui Duan
Summary: We have developed an efficient palladium-catalyzed denitrative N-arylation method, which enables the cross-coupling of N-H heteroarenes with nitroarenes. This method allows for the selective synthesis of various functionalized N-arylated heterocycles with moderate to excellent yields. Furthermore, its success in scale-up experiments and late-stage modification of natural products and pharmaceutical derivatives demonstrates the synthetic potential of this direct denitrative N-arylation protocol in synthetic chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yu-Cheng Hsu, Ming-Tsz Chen
Summary: The N-heterocyclic carbene-palladium(II) amine complexes synthesized in this study showed good catalytic activities for the Buchwald-Hartwig amination reaction of aryl chlorides, yielding 21 expected coupling products in moderate to high yields under mild conditions. The complexes were characterized by single crystal X-ray diffraction and NMR spectroscopy, and the reactions were conducted in air without purification of starting materials.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Steven B. Coffey, David J. Bernhardson, Stephen W. Wright
Summary: BippyPhos shows high catalytic efficiency in Buchwald - Hartwig amination reactions. However, its wider application is limited by the lack of readily available precatalysts. In this study, we report the gram-scale synthesis and characterization of isopropylBippyPhos, and its conversion to isopropylBippyPhos Pd G2, a biaryl phosphine precatalyst. We demonstrate the competence of isopropylBippyPhos Pd G2 in palladium-catalyzed Buchwald - Hartwig amination reactions and Suzuki - Miyaura cross-coupling reactions.
Article
Chemistry, Organic
Tian Cao, Yi-Peng Luo, Long Cheng, Jia-Li Zhao, Qiao-Sen Jia, Shu Zhang, Xiang-Wei Liu
Summary: This article describes a novel method for the de novo catalytic synthesis of diarylamines through a palladium-catalyzed reductive Buchwald-Hartwig amination of nitroarenes with aryl (pseudo)halides. The use of upstream nitroarenes as arylamine surrogates, the choice of bis(pinacolato)diboron (B(2)pin(2)) as a stoichiometric reducing agent, and the wide scope of substrates including (hetero)aryl halides (Cl, Br, and I) and aryl triflates are the notable features of this protocol. Furthermore, its successful application in the synthesis of advanced intermediates and active pharmaceutical ingredients provides an alternative and cost-effective approach to the synthesis of diarylamine-incorporated molecules. Preliminary mechanistic investigations suggest the involvement of amine and nitrosoarene intermediates in this reductive process.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Junxin Rao, Xiaoyu Ren, Xin Zhu, Zhen Guo, Chengming Wang, Cong-Ying Zhou
Summary: In this study, a Ru(ii)-catalyzed C-N cross-coupling reaction of diazoquinones with arylamines was reported, providing access to functionalized diarylamines with high yields under mild and neutral conditions. The synthetic utility of this method was demonstrated by the modular synthesis of structurally sophisticated diarylamine derivatives and the short synthesis of an anti-inflammatory compound.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Polymer Science
Chinnadurai Satheeshkumar, Bum-Joon Jung, Hansol Jang, Wonhee Lee, Myungeun Seo
Summary: Surface modification using Buchwald-Hartwig amination allows for the introduction of primary amine groups onto polymer surfaces, providing a facile and recyclable method for their installation. Covalent bonding between substrates via amine-isocyanate chemistry results in higher bonding strength compared to previous noncovalent methods.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Zi-Chao Wang, Yan-Yu Li, Shuo-Qing Zhang, Xin Hong, Shi-Liang Shi
Summary: This article reports a highly efficient nickel catalyst for the arylation of sterically hindered primary and secondary amines with aryl chlorides or phenol derivatives, enabled by an unsymmetric N-heterocyclic carbene ligand. The method is general, efficient, and scalable, providing excellent yields of various sterically demanding anilines under mild conditions. Computational studies suggest that the unsymmetric bulky and flexible N-heterocyclic carbene ligand plays a critical role in balancing the oxidative addition and reductive elimination steps.
Article
Chemistry, Multidisciplinary
Xuexue Dong, Yiying Yang, Yang Shen, Aihua Yuan, Zengjing Guo, Heng Song, Fu Yang
Summary: In this study, a light-mediated reductive C-N coupling method for nitroaromatic compounds without the use of a catalyst and harsh reaction conditions is demonstrated. The effectiveness of photothermal synergy catalysis was further validated.
Article
Chemistry, Organic
Pablo Gomez-Orellana, Agusti Lledos, Gregori Ujaque
Summary: The Buchwald-Hartwig amination of arylhalides with the Pd-Josiphos complex using ammonia as a reactant is a useful process for primary amine synthesis. Density-functional theory calculations were used to examine the reaction mechanism, revealing the importance of the chelate phosphine ligand and base in the process. The study allowed for the proposal of a complete reaction mechanism for the Pd-catalyzed C-N coupling reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Yaxu Liu, Thomas Scattolin, Alberto Gobbo, Marek Belis, Kristof Van Hecke, Steven P. Nolan, Catherine S. J. Cazin
Summary: The synthesis of a series of stable Pd(II)-NHC pre-catalysts with excellent catalytic activity in Suzuki-Miyaura and Buchwald-Hartwig reactions has been successfully achieved in this study, especially when IPrCl is employed as an ancillary ligand. The [Pd(IPr*)Cl(1-Bu-t-indenyl)] complex also exhibited optimal catalytic activity in the challenging Suzuki-Miyaura reaction between esters and arylboronic acids under very mild reaction conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Vinzenz Thoennissen, Frederic W. Patureau
Summary: The atroposelective formation of C-N bonds has recently become a hot topic within the field of amination reactions, as it is surprising that enantioselective solutions have been lacking in this ancient class of organic coupling reactions despite the maturity of asymmetric synthesis as a concept and field. Some promising examples hint at an imminent change of paradigm.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Nazaret Santamaria, Clara Velasco, Mario Marin, Celia Maya, M. Carmen Nicasio
Summary: In this study, a series of LPdCl2(amine) complexes bearing dialkylterphenyl phosphanes (PR2Ar ') and pyridine or morpholine ligands were synthesized and characterized. These novel compounds were tested as precatalysts in aryl amination reactions. The complex [(PCyp(2)Ar(Xyl2))PdCl2(morpholine)] exhibited the best catalytic activity, enabling the room-temperature coupling of aryl bromides and chlorides with aniline.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Yue Tang, Idir Benaissa, Mathieu Huynh, Laure Vendier, Noel Lugan, Stephanie Bastin, Philippe Belmont, Vincent Cesar, Veronique Michelet
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Inorganic & Nuclear
Alina A. Grineva, Oleg A. Filippov, Sergei E. Nefedov, Noel Lugan, Vincent Cesar, Dmitry A. Valyaev
Article
Chemistry, Multidisciplinary
Idir Benaissa, Lenka Pallova, Marie-Emilie Morantin, Thomas Lafitte, Mathieu Huynh, Cecile Barthes, Laure Vendier, Noel Lugan, Stephanie Bastin, Vincent Cesar
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Anna Bonfiglio, Lenka Pallova, Vincent Cesar, Christophe Gourlaouen, Stephane Bellemin-Laponnaz, Chantal Daniel, Federico Polo, Matteo Mauro
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Inorganic & Nuclear
Alina A. Grineva, Oleg A. Filippov, Yves Canac, Jean-Baptiste Sortais, Sergei E. Nefedov, Noel Lugan, Vincent Cesar, Dmitry A. Valyaev
Summary: The study involved lithiation and transmetalation to prepare a heterobimetallic complex with an anionic ditopic imidazol-2,4-diylidene ligand, which was further converted to a bis(iron) complex with metalated carbenic groups. It was found that metalation significantly affects the electronic donation properties of the ligand.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lenka Pallova, Etienne S. Gauthier, Laura Abella, Marion Jean, Nicolas Vanthuyne, Vincent Dorcet, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: This study describes the straightforward synthesis of partially saturated H-6-fluoreno[n]helicenes and their chiroptical properties. The key cyclization step involves an intramolecular McMurry reaction, and chiral stationary phase HPLC analysis confirms the stability of the configuration of the compounds at room temperature. Additionally, the chiroptical properties of the enantiopure compounds have been analyzed through quantum-chemical calculations, confirming their helicoidal nature.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Idir Benaissa, Katarzyna Gajda, Laure Vendier, Noel Lugan, Anna Kajetanowicz, Karol Grela, Veronique Michelet, Vincent Cesar, Stephanie Bastin
Summary: The coordination chemistry of anionic NHC based on an IPy platform substituted at the CS position was studied with transition-metal centers, showing different coordination modes and reaction mechanisms. A gold(I) intermediate was also discovered during the process and structurally characterized. These complexes exhibited high activities and a large tolerance towards functional groups in the synthesis of carboxylic acid derivatives.
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, Multidisciplinary
Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cecile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stephanie Bastin, Vincent Cesar
Summary: The first efficient chiral helicene-NHC gold(I) complexes for enantioselective catalysis have been synthesized. Their structural and stereochemical characterization confirms their potential in asymmetric catalysis, demonstrated by the benchmark cycloisomerization reaction with high enantiomeric excess.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Biochemistry & Molecular Biology
Mirko Ruamps, Stephanie Bastin, Lionel Rechignat, Alix Sournia-Saquet, Laure Vendier, Noel Lugan, Jean-Marie Mouesca, Dmitry A. Valyaev, Vincent Maurel, Vincent Cesar
Summary: The coordination chemistry of the N-heterocyclic carbene ligand IMes((NMe2)2), and its interaction with transition metal centers, was investigated. The redox behavior of the resulting organometallic complexes was studied, revealing the different oxidation states and their effects on the donating properties of the ligand.
Review
Chemistry, Multidisciplinary
Paul Teixeira, Stephanie Bastin, Vincent Cesar
Summary: N-heterocyclic carbene (NHC) ligands have gained considerable importance in gold catalysis due to their appealing properties. Fused polyaromatic NHCs, featuring fused aromatic rings, have attracted wider attention in recent years for their unique structural and electronic properties. These versatile platforms offer superior activity and/or selectivity in NHC-gold catalysis and provide opportunities for further functionalization, chirality introduction, stimuli-responsiveness, or cooperativity within the NHC-gold systems.
ISRAEL JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ajay Padunnappattu, Carine Duhayon, Vincent Cesar, Yves Canac
Summary: In this study, a tricationic imidazolium salt with two N-cyclopropenio substituents was prepared using the onio-substitution strategy. The electronic properties of the related dicationic NHC were evaluated, and it was found to be one of the least-donating cationic NHCs reported so far. The ability of this compound to coordinate with Pd(II) and Au(I) centers was also investigated, and corresponding complexes were characterized.
Article
Chemistry, Inorganic & Nuclear
Remy Brousses, Vincent Maurel, Jean-Marie Mouesca, Vincent Cesar, Noel Lugan, Dmitry A. Valyaev
Summary: The oxidation of half-sandwich Mn-I complexes Cp(CO)(2)Mn(NHC) bearing various N-heterocyclic carbene ligands resulted in the isolation of stable Mn-II radical cations in high yield. Systematic X-ray diffraction studies revealed structural changes upon oxidation, and ESR spectra allowed for the identification of complex conformers and structural assignment using DFT calculations. The promising applications of these redox-active organometallic fragments lie in their stability in both metal oxidation states, moderate oxidation potentials, and ease of detection using various spectroscopic techniques.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Cecile Barthes, Carine Duhayon, Yves Canac, Vincent Cesar
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Antoine Bruneau-Voisine, Lenka Pallova, Stephanie Bastin, Vincent Cesar, Jean-Baptiste Sortais
CHEMICAL COMMUNICATIONS
(2019)
