Article
Chemistry, Multidisciplinary
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis has the potential to achieve oxidative and oxygenative transformations, generating various NHC-bound intermediates and enabling non-umpolung processes through the activation of carbon atoms and heteroatoms. This review aims to discuss the recent developments in the field of oxidative NHC catalysis since 2014, with a focus on pivotal intermediates and their mechanistic involvement. More details can be found in the review article by C. De Risi and co-workers.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Carmela De Risi, Arianna Brandolese, Graziano Di Carmine, Daniele Ragno, Alessandro Massi, Olga Bortolini
Summary: Oxidative N-heterocyclic carbene (NHC) catalysis enables oxidative and oxygenative transformations, producing various NHC-bound intermediates and facilitating non-umpolung processes by activating carbon atoms and heteroatoms. This review discusses the developments in the literature on oxidative NHC catalysis since 2014, with a specific focus on pivotal intermediates and their mechanistic involvement.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Leonard Karl, Jan Meisner, Christian Ganter
Summary: Attempts were made to synthesize two novel four-membered 1,3-diazetidine based N-heterocyclic carbenes (NHCs) with an organic backbone and a carbonyl functionality. Although the isolated carbenes were not achieved, their respective carbene dimers were obtained in quantitative yield and underwent degradation and rearrangement upon thermal exposure. Some of the thermal reaction species were isolated and characterized, while others were observed using mass spectrometry. Ab initio and density functional theory (DFT) calculations provided a mechanistic explanation for the experimental observations. Classic carbene trapping reactions are still a goal to be achieved due to the strong preference for dimerization.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Vallyanga Chalil Rojisha, Indu Purushothaman, Susmita De, Pattiyil Parameswaran
Summary: The C-N bonds in N-heterocyclic carbene are best described as one sigma-type 3c-2e electron sharing bond and one sigma-type 3c-2e donor-acceptor bond, which are equivalent to two localized representations.
CHEMICAL PHYSICS LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Chun-Lin Zhang, Yuan-Yuan Gao, Hai-Ying Wang, Bang-An Zhou, Song Ye
Summary: An NHC-catalyzed de novo synthesis method for axially chiral benzothiophene/benzofuran-fused biaryls has been reported, providing a convenient and efficient access to these compounds with high enantioselectivities. The method also works well for the synthesis of tetra-ortho-substituted biaryls, addressing an unsolved problem in the field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Simiao Zhang, Xiaoxue Wang, Li-Li Han, Jibin Li, Zheng Liang, Donghui Wei, Ding Du
Summary: Atropisomers bearing multiple stereogenic axes have become increasingly important in material science, pharmaceuticals, and catalysis. However, the construction of multi-axis atropisomers with high stereoselectivity remains rare and challenging. In this study, a new class of 1,2-diaxially chiral triaryl alpha-pyranones was successfully synthesized in a single-step reaction, demonstrating broad substrate scope and excellent stereo-control. The success of this reaction can be attributed to the rational design of structurally matched reaction partners and the careful selection of the asymmetric catalytic system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Guangjin Zhen, Kai Jiang, Biaolin Yin
Summary: Dearomative reactions enable the concise assembly of highly functionalized three-dimensional molecules by disrupting the aromaticity of starting materials. N-heterocyclic carbenes (NHCs) have emerged as powerful catalysts for dearomatization reactions, allowing for the construction of natural product and drug skeletons. This overview summarizes the progress in NHC-catalyzed dearomative reactions, classifying the reactions by modes and categories of intermediates and providing representative mechanisms.
Article
Chemistry, Multidisciplinary
Tingting Li, Chengli Mou, Puying Qi, Xiaolin Peng, Shichun Jiang, Gefei Hao, Wei Xue, Song Yang, Lin Hao, Yonggui Robin Chi, Zhichao Jin
Summary: A catalytic atroposelective cycloaddition reaction between thioureas and ynals has been developed, enabling the establishment of C-N axial chirality with excellent optical purities. The resulting axially chiral thiazine derivative products contain multiple functional groups and are suitable for further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jin Hyun Park, Sun Bu Lee, Byeong Jun Koo, Han Yong Bae
Summary: A water-accelerated, N-heterocyclic carbene (NHC)-catalyzed aza-Michael addition reaction was reported for the synthesis of beta-aminosulfonyl fluorides, key components of the SuFEx reaction. Water as a reaction medium significantly enhanced the reaction rate and demonstrated late-stage ligation with bioactive molecules.
Review
Chemistry, Multidisciplinary
Qing-Zhu Li, Rong Zeng, Bo Han, Jun-Long Li
Summary: In recent years, the N-heterocyclic carbene (NHC) organocatalysis field has seen the emergence of long-awaited single-electron transfer (SET) reactions, providing opportunities to develop new catalytic modes and useful synthetic methods.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Zheng-Wang Qu, Hui Zhu, Rainer Streubel, Stefan Grimme
Summary: Extensive DFT calculations in this study show that the isomerization of unprotected C-5-position mesoionic N-heterocyclic olefins (mNHOs) can be efficiently catalyzed by weakly protic acidic species, including mNHOs themselves, their Lewis adducts, and polar H2O molecules, leading to the formation of more Lewis-basic mesoionic carbenes (MICs) and enabling catalytic isomerization and H-isotope exchange of mNHOs and their Lewis adducts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Biochemistry & Molecular Biology
Camilo Morales-Manrique, Edwin A. Baquero, James Guevara-Pulido
Summary: In recent years, N-heterocyclic carbenes (NHCs) have been recognized as versatile organocatalysts for the activation of aldehydes, leading to the production of 3,4-dihydropyran-2-ones and related derivatives. This review provides an overview of the organocatalytic processes involving NHCs in synthesizing these compounds over the past eight years. These processes utilize various substrates, catalysts, and reaction conditions, mainly focusing on [4+2] and [3+3] cycloadditions to generate the desired skeleton with biological activity and multiple stereocenters. The resulting products can be scaled up and further modified for potential applications in the field of biology.
Article
Chemistry, Physical
Mali Zhou, Jianjian Liu, Rui Deng, Qingyun Wang, Shuquan Wu, Pengcheng Zheng, Yonggui Robin Chi
Summary: A catalytic strategy for asymmetric synthesis of chiral tetrasubstituted silicon-stereogenic silanes is disclosed. By using a covalently symmetric silane as the substrate and a N-heterocyclic carbene catalyst, the substrate can be selectively activated and undergo desymmetrization reaction to afford optically enriched products.
Article
Chemistry, Multidisciplinary
Juan J. Navarro, Mowpriya Das, Sergio Tosoni, Felix Landwehr, Maximilian Koy, Markus Heyde, Gianfranco Pacchioni, Frank Glorius, Beatriz Roldan Cuenya
Summary: N-Heterocyclic carbenes (NHCs) show superior properties in self-assembled monolayers (SAMs) and understanding the influence of the substrate on the molecular arrangement is crucial. This study reveals that on Cu(100), NHCs form mostly disordered phases, while on Cu(111), well-defined structures ranging from magic-number islands to molecular ribbons are observed. Diffusion and commensurability play a key role in determining the observed arrangements, providing insights into molecule-substrate interaction and the potential for tuning nanopatterned structures based on NHC assemblies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Palak Garg, Ambre Carpentier, Iskander Douair, Deepak Dange, Yixiao Jiang, K. Yuvaraj, Laurent Maron, Cameron Jones
Summary: The reaction of 1,2-disilylene with CO was investigated, and the resulting bis(silylene) compound exhibits a structure similar to abnormal N-heterocyclic carbenes. The coordination complexes of the bis(silylene) could potentially serve as catalysts for organic transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Bogdan Ya. Karlinskii, Valentine P. P. Ananikov
Summary: With fossil resources depleting at a rapid pace, researchers in the fields of chemistry and materials science are increasingly turning to renewable sources and corresponding technologies. Sustainable materials science has gained significant interest due to the development of new polymers with desired properties. This review summarizes recent scientific reports on the synthesis, construction, and computational studies of novel sustainable polymeric materials containing (pseudo)aromatic furan cores. Linear polymers for thermoplastics, branched polymers for thermosets, and other crosslinked materials are emerging as key materials. Polymer blends and composites based on sustainable polyfurans are also considered as pathways to achieve high-value-added products.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Daria V. Chernysheva, Ekaterina A. Sidash, Maksim S. Konstantinov, Victor A. Klushin, Denis V. Tokarev, Veronica E. Andreeva, Evgeny A. Kolesnikov, Vasily V. Kaichev, Nina V. Smirnova, Valentine P. Ananikov
Summary: Sustainable human development requires reducing the cost of energy storage. The conversion of waste materials into high-value-added carbon materials is well developed for solid wastes, but more challenging for liquid wastes. In this study, a new approach was developed to convert liquid waste into solid materials with nitrogen incorporation. The obtained carbon materials for energy storage exhibited superior characteristics under simple process conditions.
Article
Chemistry, Multidisciplinary
Gleb M. Averochkin, Evgeniy G. Gordeev, Fedor A. Kucherov, Valentine P. Ananikov
Summary: A new approach to the use of plant biomass in organic synthesis has been developed, resulting in a significant increase in molecular complexity through a cascade cycloaddition reaction of biobased 5-HMF derivatives. The reaction proceeds under thermodynamic control, providing rapid access to high complexity compounds. Quantum chemical calculations were used to study the reaction pathways and reveal the major factors influencing selectivity. This study highlights the potential of oligomeric derivatives as valuable materials for the synthesis of nonplanar scaffolds.
Article
Multidisciplinary Sciences
Indrajit Ghosh, Nikita Shlapakov, Tobias A. Karl, Jonas Dueker, Maksim Nikitin, Julia V. Burykina, Valentine P. Ananikov, Burkhard Koenig
Summary: Adaptive dynamic homogeneous catalysis (AD-HoC) with nickel under visible-light-driven redox reaction conditions allows for general C(sp(2))-(hetero)atom coupling reactions with various nucleophiles. The self-adjustive nature of the catalytic system simplifies the classification and optimization process, resulting in predictable reaction conditions and hundreds of synthetic examples.
Article
Chemistry, Applied
Kirill S. S. Erokhin, Valentine P. P. Ananikov
Summary: Preparation and implementation of chemical reactions often require large laboratory space. In this study, the researchers successfully miniaturized laboratory equipment by optimizing the spatial arrangement of functional parts. They developed a compact acetylene generation cartridge that was sealed using 3D printing and suitable for long-term storage. The cartridge also demonstrated high efficiency in synthesizing bis(arylthio)-substituted ethenes and 1,2-bis(alkylthio)ethenes.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexey. S. S. Galushko, Valentina. V. V. Ilyushenkova, Julia. V. V. Burykina, Ruslan. R. R. Shaydullin, Evgeniy. O. O. Pentsak, Valentine. P. P. Ananikov
Summary: Understanding the interaction between soluble metal complexes and supported metal particles is significant for elucidating the reaction mechanisms in highly active homogeneous transition metal catalysts. In this study, we reveal that the deposited particles on a carbon surface formed from a soluble Pd(0) complex exhibit more richness than previously assumed, even with a simple experimental procedure. We demonstrate that highly active hidden metal centers are formed and leached out by the solvent, showing diverse reactivity in solution. These results suggest that trace amounts of molecular monometallic centers can naturally exist in heterogeneous catalysts and be easily transformed into homogeneous catalytic systems.
Editorial Material
Chemistry, Inorganic & Nuclear
Valentine Ananikov, Vladimir Gevorgyan, Christina Moberg, Michinori Suginome, Anna Trzeciak
Article
Chemistry, Multidisciplinary
Victoria A. Korabelnikova, Evgeniy G. Gordeev, Valentine P. Ananikov
Summary: The discovery of high-performance thermoplastics has led to the development of fused filament fabrication technology, particularly in the field of chemical laboratory practice. This study focuses on the properties of various general purpose plastics, plastics with high chemical resistance, and plastics with increased chemical and heat resistance based on polyamides. It is found that carbon-filled polyamide-6 is an excellent material for the design of chemical reactors in laboratory practice. A new method for complex testing of FFF parts is developed, allowing simultaneous consideration of multiple external factors. The tests of chemical reactors made of PA6-CF demonstrate the high efficiency of this material for the manufacturing of chemical equipment.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Roman O. Pankov, Darya O. Prima, Alexander Yu. Kostyukovich, Mikhail E. Minyaev, Valentine P. Ananikov
Summary: Pd/NHC complexes with electron-withdrawing halogen groups were synthesized, and their effect on the Pd-NHC bond was evaluated. The optimized synthetic approach enabled the incorporation of o-, m-, and p-XC6H4-substituted NHC ligands into Pd complexes (X = F, Cl, Br, CF3). The catalytic activity of the obtained Pd/NHC complexes was compared in the Mizoroki-Heck reaction, showing a significant increase in performance for Br and CF3 substituents.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Applied
Yasuaki Fukazawa, Vladimir Yu. Vaganov, Julia V. Burykina, Artem N. Fakhrutdinov, Ruslan I. Safiullin, Felix Plasser, Aleksandr E. Rubtsov, Valentine P. Ananikov, Andrei V. Malkov
Summary: The mechanism of metal-catalyzed asymmetric alkylation of indoles remains uncertain. In this study, the authors investigate the mechanism from both molecular and nano-level perspectives, revealing the role of water and catalyst precursor on reaction selectivity and performance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Konstantin S. Kozlov, Daniil A. Boiko, Elena V. Detusheva, Konstantin V. Detushev, Evgeniy O. Pentsak, Anatoly N. Vereshchagin, Valentine P. Ananikov
Summary: Microbial interactions and biofilm formation have significant societal relevance and studying these processes require efficient imaging and analysis methods. This study proposes the use of automated scanning electron microscopy and deep neural networks for in-depth analysis and mapping of biofilms. The approach was evaluated using a newly prepared annotated dataset and showed promising results in terms of data analysis and characterization of biofilms.
Review
Chemistry, Multidisciplinary
Roman M. Mironenko, Dmitry B. Eremin, Valentine P. Ananikov
Summary: This review addresses the issue of dead metal in heterogeneous metal catalysts, analyzing the factors contributing to its formation and proposing strategies to mitigate its occurrence. The study is important for improving catalyst preparation and optimizing catalyst performance, and has broad implications for various scientific disciplines.
Article
Chemistry, Physical
Evgeniia E. Ondar, Alexander Yu. Kostyukovich, Julia V. Burykina, Alexey S. Galushko, Valentine P. Ananikov
Summary: Recent developments have shown that a potent catalytic system can be created without the need for complex and costly organic ligands with transition metal compounds. By following the principles of dynamic catalysis, a simpler approach involving the use of regular complexes as catalyst precursors under carefully chosen reaction conditions is feasible. This approach allows for the dynamic transformations of the metal compounds, resulting in a catalyst system with acceptable selectivity and impressive performance characteristics.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
