Review
Chemistry, Physical
Javier Corpas, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: This paper discusses the importance of the catalytic functionalization of alkynes with organoboron reagents in synthesis and the latest research progress, including innovations in asymmetric internal alkynes, stereochemistry, and metal migration. It focuses on the practicality, limitations, and challenges for future research of the mechanisms and synthetic methods.
Review
Chemistry, Inorganic & Nuclear
Chong-Yang Shi, Long Li, Wei Kang, Yan-Xin Zheng, Long-Wu Ye
Summary: The efficient and selective construction of carbon-carbon bond in an atom-economic and mild way remains a core aspect of modern organic synthesis. The strategy of Claisen rearrangement triggered by catalytic alkyne alkoxylation has unique advantages and has attracted widespread attention in the past two decades. Both intramolecular and intermolecular protocols provide practical and facile approaches for the synthesis of complex compounds with valuable core skeletons.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Biochemistry & Molecular Biology
Lianfen Chen, Chaoyi Zhao, Weixian Mo, Chunsheng Li, Xiaoming Lin
Summary: A facile and efficient methodology using a dirhodium metal-organic cage as a heterogeneous catalyst was demonstrated for the generation of C-X (X = Si, B) bond through a carbene insertion process. Functionalized alkynes served as safe carbene precursors and yielded Si-H and B-H insertion products in moderate to excellent yields. The reactions showed high atom-economy, broad substrate scope, and mild reaction conditions. The MOC-Rh-1 catalyst could be easily recovered and reused without significant loss in activity.
Article
Chemistry, Multidisciplinary
Jingfeng Huo, Kangbao Zhong, Yazhen Xue, MyeeMay Lyu, Yifan Ping, Wenbai Ouyang, Zhenxing Liu, Yu Lan, Jianbo Wang
Summary: In this study, a highly efficient palladium-catalyzed carbene insertion reaction into strained Si-C bonds of benzosilacyclobutanes was reported, providing an efficient method for accessing alpha-chiral silanes. It was found that with a sterically hindered ligand, the carbene insertion occurred selectively on the C(sp(3))-Si bond of benzosilacyclobutanes with excellent site- and enantioselectivity, while selectively occurred on the C(sp(2))-Si bond with less sterically hindered ligands. The reaction mechanism, particularly the roles of chiral ligands in controlling the site-selectivity of the insertion reactions, was elucidated using hybrid density functional theory.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Physical
Shengnan Lin, Tingan Zhang
Summary: This paper focuses on the synthetic methods of metal spinel oxides (MSOs) and their applications in adsorption catalysis, magnetic materials, electrodes, and sensors. The modifications and applications of AB2O4 (M > 2, B = Al, Fe, Co, and Mn) MSOs are compared. The advantages and disadvantages of MSO synthetic methods are briefly introduced and discussed. The future development trends and application extensions for MSO syntheses are also discussed.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Polymer Science
Thi Tran, Loi H. Do
Summary: This review article provides an overview of various methods for regulating the polymerization of olefins using transition metal complexes, including catalyst tuning through reaction engineering and introduction of external stimuli. The unique capabilities and limitations of different approaches are discussed, along with the potential impacts of externally regulated polymerization on applications and future research.
EUROPEAN POLYMER JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Danijela Lunic, Enrico Bergamaschi, Christopher J. Teskey
Summary: Light, in combination with transition metal catalysis, can modify catalyst function in a non-invasive manner, often switching on or accelerating reactions that do not occur in the dark. While it is less common, the ability to completely change reactivity or selectivity between different reaction outcomes is also possible with these systems. These non-natural, photo-switchable systems provide key mechanistic insights that enhance our understanding and stimulate the development of new catalytic activities, potentially impacting fields such as polymer chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Teng Yuan, Qi Tang, Chuan Shan, Xiaohan Ye, Jin Wang, Pengyi Zhao, Lukasz Wojtas, Nicholas Hadler, Hao Chen, Xiaodong Shi
Summary: This study presents a novel method for alkyne trifunctionalization through gold catalysis, achieving consecutive reactions with high efficiency and excellent yields under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Paul L. Kress, Shengjie Zhang, Yicheng Wang, Volkan Cinar, Cynthia M. Friend, E. Charles H. Sykes, Matthew M. Montemore
Summary: Single-atom catalysts have limitations in facilitating reactions that require multiple adjacent sites. This study introduces trimetallic dual-atom alloys as a new class of catalysts with desirable reactivity. Experimental evidence shows that Pt-Cr sites in Ag(111) can catalyze the conversion of ethanol, while PtAg and CrAg are unreactive. The discovery of thermodynamically favorable dual-atom alloy sites opens up new possibilities for creating materials with enhanced chemical reactivity beyond the single-atom paradigm.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Jasnoor S. Mann, Binh Khanh Mai, Thanh Vinh Nguyen
Summary: The carbonyl-alkyne metathesis (CAM) reaction is a versatile method to access alpha,beta-unsaturated carbonyl compounds, which are important precursors and structural motifs in biologically active substances. We developed an efficient organic Lewis acid catalytic system that promotes both intramolecular and intermolecular CAM reactions. Our metal-free protocol can produce a diverse family of useful organic structures from a broad range of substrates.
Article
Chemistry, Multidisciplinary
Claudia E. Berdugo-Diaz, Melissa T. Manetsch, Yang Sik Yun, Jieun Lee, Jing Luo, Xue Chen, David W. Flaherty
Summary: Esters can be reduced to ethers and alcohols through C-O bond cleavage by hydrogenation and hydrogenolysis pathways on Bronsted acidic faujasite (M-FAU) supported metal nanoparticles. The rates and selectivities of each pathway are influenced by the metal identity (M=Co, Ni, Cu, Ru, Rh, Pd, and Pt). Pt-FAU catalyst exhibits propyl acetate consumption rates up to 100 times higher than other M-FAU catalysts and achieves a 34% selectivity for ethyl propyl ether. The reduction of esters appears to involve a bifunctional mechanism, with stepwise addition of H* atoms to the carbonyl to form hemiacetals on the metal sites, followed by hemiacetal diffusion to Bronsted acid sites for dehydration to ethers or decomposition to alcohol and aldehyde. The reduction rates of propyl acetate seem to be determined by H* addition to the carbonyl and C-O cleavage of hemiacetal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Yichen Wu, Peng Wang
Summary: Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry. Monohydrosilanes, which bear a Si-H bond, are especially unique due to their facile transformations through stereospecific bond-formation reactions. In addition, they have also been used as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, and potential optoelectronic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Multidisciplinary Sciences
Chiara Costabile, Stefania Pragliola, Fabia Grisi
Summary: The last decades have witnessed the rapid growth of applications of N-heterocyclic carbenes (NHCs) in various chemistry fields. Due to their unique properties, NHCs have become a powerful tool in coordination chemistry, particularly in the synthesis of stable metal-ligand frameworks with main group metals and transition metals. This article provides an overview of the use of five-membered monodentate C-2-symmetric N-heterocyclic carbenes (NHCs) as ligands for transition-metal complexes and highlights their most relevant applications in asymmetric catalysis.
Article
Chemistry, Physical
Ran Bu, Lin Zhang, Lu-Lu Gao, Weng-Jie Sun, Shuai-Liang Yang, En-Qing Gao
Summary: The study developed a TpBpy-supported Cu(I) catalyst that can efficiently catalyze the conversion of CO2 and terminal alkynes to propiolic acids. The catalytic activity arises from the synergy between the organic framework of TpBpy and the Cu(I) sites, with the organic framework also possessing its own catalytic activity.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Igor Zayakin, Evgeny Tretyakov, Anna Akyeva, Mikhail Syroeshkin, Julia Burykina, Andrey Dmitrenok, Alexander Korlyukov, Darina Nasyrova, Irina Bagryanskaya, Dmitri Stass, Valentine Ananikov
Summary: Nitronyl nitroxides are important functional building blocks that can be used for molecular-level optimization and nano-scale device development. Efficient synthetic approaches for these compounds are still challenging.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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
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, Physical
Liliya T. Sahharova, Julia V. Burykina, Alexander Yu. Kostyukovich, Dmitry B. Eremin, Daniil A. Boiko, Artem N. Fakhrutdinov, Valentine P. Ananikov
Summary: The common assumption that dimeric metal complexes in catalytic systems are not directly involved in catalytic processes was proven wrong through experimental and theoretical study. The on-cycle participation of dimeric metal complexes and their advantageous performance in terms of improved selectivity were observed. A conceptual rationalization for the participation of dimeric species in the catalytic cycle was developed.
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.
Article
Nanoscience & Nanotechnology
Olga A. Kamanina, Elizaveta A. Lantsova, Pavel V. Rybochkin, Vyacheslav A. Arlyapov, Evgeniya A. Saverina, Natalia S. Kulikovskaya, Alexander M. Perepukhov, Anatoly N. Vereshchagin, Valentine P. Ananikov
Summary: This study presents a novel hybrid biocatalyst design that combines the individual efficiency of microorganisms while avoiding negative interactions between them. The immobilized microorganism mixture showed excellent performance in determining the biochemical oxygen demand in real water samples.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Editorial Material
Chemistry, Inorganic & Nuclear
Valentine Ananikov, Vladimir Gevorgyan, Christina Moberg, Michinori Suginome, Anna Trzeciak
Article
Chemistry, Multidisciplinary
Alexey S. Kashin, Darya O. Prima, Daria M. Arkhipova, Valentine P. Ananikov
Summary: Using SEM and TEM techniques, the transformations of palladium-containing species in imidazolium ionic liquids are studied, revealing the correlation between the reactivity of aryl halides and the microdomain structure. It is found that the formation of a stable nanosized palladium phase is detected under the action of aryl halides capable of forming microcompartments. This work highlights the importance of considering both molecular and microscale properties in catalytic transformations.
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)
