Article
Chemistry, Multidisciplinary
Yaroslav K. Shtaitz, Aluru Rammohan, Alexey P. Krinochkin, Evgeny D. Ladin, Ilya I. Butorin, Nataliya N. Mochulskaya, Igor A. Khalymbadzha, Pavel A. Slepukhin, Vadim A. Shevyrin, Dmitry S. Kopchuk, Grigory V. Zyryanov, Oleg N. Chupakhin
Summary: A solvent-free reaction between C6-unsubstituted 5-aryl-1,2,4-triazines and 2-amino-4-aryloxazoles at high temperature was studied. The reaction proceeds via inverse electron demand aza-Diels-Alder reaction and shows highly regioselective formation of 3,6-diarylpyridines in up to 60% isolated yield. The synthetic approach demonstrates valuable advantages of high regioselectivity and solvent-free conditions.
Article
Chemistry, Organic
Julia O. Strelnikova, Alexander N. Koronatov, Nikolai Rostovskii, Alexander F. Khlebnikov, Olesya Khoroshilova, Mariya A. Kryukova, Mikhail S. Novikov
Summary: The domino reaction catalyzed by Rh-2(Piv)(4) leads to the formation of N-sulfonylated (Z)-2-(2-aminovinyl)imidazoles, providing a direct and flexible access to the desired compounds.
Article
Chemistry, Physical
Ying Liang, Meng Xia, Yuxiang Zhao, Dong Wang, Yongpeng Li, Zhuyin Sui, Juanxiu Xiao, Qi Chen
Summary: The development of functional covalent organic frameworks is a new research field. In this work, COF-SQ-Ph with extended pi-conjugated structure and enhanced stability was used for sulfur cathodes in lithium-sulfur batteries. The cycloaddition reaction in flask for triazine-based COFs could promote large-scale preparation and post-synthesis modification of COFs.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Luca De Angelis, Graham C. Haug, Gildardo Rivera, Soumen Biswas, Ammar Al-Sayyed, Hadi Arman, Oleg Larionov, Michael P. Doyle
Summary: One important reaction of 1,2,3-triazines is the inverse electron demand Diels-Alder (IEDDA) cycloaddition with a dienophile, which proceeds through nucleophilic addition to the triazine followed by N-2 loss and cyclization. Previous studies have not provided a comprehensive understanding of the site of nucleophilic addition on the triazine. This study investigated the C-, N-, H-, O-, and S-nucleophilic additions on 1,2,3-triazine and 1,2,3-triazine-1-oxide frameworks and revealed the differentiation of addition at the 4- and 6-positions. Computational studies further examined the factors influencing the outcomes of these reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yi-Min Fan, Josemon George, Jiao Yu J. Wang, Michael G. Gardiner, Michelle L. Coote, Michael S. Sherburn
Summary: Through the study, it was found that imines can participate in intermolecular formal [4 + 2] cycloadditions with dendralenes, forming hexahydro- and octahydro-isoquinoline structures. After optimizing the conditions, the formal aza-Diels-Alder reaction proceeds with high regio- and stereoselectivity.
Article
Chemistry, Multidisciplinary
Shannon E. Creegan, Matthias Zeller, Edward F. C. Byrd, Davin G. Piercey
Summary: 3,5-Diamino-6-nitro-1,2,4-triazine (DANT) was identified as a potentially insensitive energetic material with high symmetry and planar geometry. The generation of this energetic material was achieved by reduction and oxidation reactions. DANT and DANTX were characterized using various analytical methods, and their structures and properties were determined.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Organic
Alexey P. Krinochkin, Yaroslav K. Shtaitz, Aluru Rammohan, Ilya I. Butorin, Maria Savchuk, Igor A. Khalymbadzha, Dmitry S. Kopchuk, Pavel A. Slepukhin, Vsevolod V. Melekhin, Anna Shcheglova, Grigory Zyryanov, Oleg N. Chupakhin
Summary: An operationally simple and highly efficient one-pot method has been developed for the synthesis of pyridines appended with pyrazole via an NH linker. The synthesized compounds showed promising in silico activity against JAK1, SYK, and FAK1 kinases. In vitro testing demonstrated significant cytotoxicity of the most promising compound against A-172 and HepG2 cancer cell lines, with IC50 values below 50 μM. The in vitro anticancer activity correlates well with the predicted in silico data.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Samuel Lauzon, Lionel Schouwey, Thierry Ollevier
Summary: A chiral ligand was successfully synthesized and its structure and configuration were determined by single-crystal diffraction analysis. The newly synthesized ligand displayed excellent catalytic activity and selectivity in iron-catalyzed asymmetric reactions.
Article
Chemistry, Organic
Rafael G. Uceda, Esther Roldan-Molina, Jorge A. R. Navarro, J. Enrique Oltra
Summary: This study explores the use of electron-deficient dienes as substrates in the aza Diels-Alder reaction, showing that the amide group significantly influences the yield of the reaction products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Christopher D. Gabbutt, B. Mark Heron, Thomas Lilly, Ochola W. Ogwang, Dimitrios Zonidis
Summary: A series of 6-styryl-1,2-oxathiine 2,2-dioxides were efficiently obtained from readily available substrates using regioselective sulfene addition and subsequent Cope elimination. Further functionalization and isomerization reactions of these compounds led to the synthesis of a variety of (hetero)aryl substituted analogues, with particular interest in the Pd-mediated direct C-H bond functionalization and silica-mediated isomerization processes.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Stephen M. Bierschenk, Judy Y. Pan, Nicholas S. Settineri, Ulrike Warzok, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste
Summary: A highly enantioselective aza-Darzens reaction catalyzed by an enantiopure supramolecular host has been discovered. Changes in enantioselectivity were observed by substituting the external chiral amide in the catalysts, and these changes were correlated to the flexibility of the supramolecular host scaffold as measured by guest exchange kinetics. By substituting the gallium(III)based host with one based on indium(III), the most flexible and selective catalyst was developed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Elisa Brambilla, Sara Leoni, Giorgio Abbiati, Valentina Pirovano, Elisabetta Rossi
Summary: Spiroindolenines were used as cyclic imine substrates in formal aza-Diels-Alder reactions with Danishefsky's diene or silyloxy-substituted electron-rich dienes, leading to the synthesis of tetrahydropyrido[1,2-a]spiroindolinones under mild conditions in the presence of ytterbium triflate as a Lewis acidic catalyst, with good yields. The reaction results in the preparation of a small library of a new class of conformational constrained heterocyclic derivatives that easily undergo selective and efficient manipulations.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Victor Laina-Martin, Jorge Humbrias-Martin, Ruben Mas-Balleste, Jose A. Fernandez-Salas, Jose Aleman
Summary: A highly efficient enantioselective inverse-electron-demand aza-Diels-Alder reaction has been developed, allowing the synthesis of benzofuran-fused 2-piperidinol derivatives with three contiguous stereocenters in a highly selective manner. Density functional theory calculations support the reaction mechanism and reveal the mode of action of the hydrogen-bond donor.
Article
Chemistry, Medicinal
Katarzyna Malarz, Dawid Zych, Robert Gawecki, Michal Kuczak, Robert Musiol, Anna Mrozek-Wilczkiewicz
Summary: Terpyridine derivatives, particularly the newly synthesized 4'-phenyl-2,2':6',2 ''-terpyridine group, exhibit high anti-proliferative activity and selective toxicity towards various types of cancer cells. Molecular biology studies have shown their impact on cell cycle inhibition, apoptosis, and autophagy pathways, with a specific focus on DNA and ROS-related targets.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Chaofan Wang, Ling Fang, Zhiyong Wang
Summary: The study reports a base-induced reaction for synthesizing tetrahydro-1,2,4-triazine derivatives, which involves the cycloaddition of two in situ generated reactive intermediates.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
A. Rammohan, A. P. Krinochkin, D. S. Kopchuk, Ya K. Shtaitz, I. S. Kovalev, M. I. Savchuk, G. V. Zyryanov, V. L. Rusinov, O. N. Chupakhin
Summary: This study tested various conditions for the inverse electron-demand aza-Diels-Alder reaction in order to obtain 4,5-diaryl-3-hydroxy-2,2'-bipyridine-6-carbonitriles from the series of 5-aryl-3-(2-pyridyl)-1,2,4-triazine-5-carbonitriles and 2-amino-4-aryloxazoles. Heating in 1,2-dichlorobenzene or under solvent-free conditions were found to be the most effective.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Alexey P. Krinochkin, Maria I. Valieva, Ekaterina S. Starnovskaya, Yaroslav K. Shtaitz, Dmitry S. Kopchuk, Olga S. Taniya, Grigory A. Kim, Vadim A. Shevyrin, Grigory V. Zyryanov, Oleg N. Chupakhin
Summary: New Tb(III) and Eu(III) complexes were synthesized using aryl-2,2'-bipyridine ligands with a cyclic DO3A chelating unit appended in the alpha position of the bipyridine core. Photophysical properties of these complexes were compared with those of complexes of ligands with an acyclic DTTA residue. The influence of the polyaminocarboxylic acid fragments on the luminescence was significant, with an increase in quantum yield observed for Eu(III) complexes and a decrease in luminescence intensity for Tb(III) complexes.
Article
Biochemistry & Molecular Biology
Nataliya V. Slovesnova, Artem S. Minin, Anna V. Belousova, Aleksey A. Ustyugov, Kirill D. Chaprov, Alexey P. Krinochkin, Maria I. Valieva, Yaroslav K. Shtaitz, Ekaterina S. Starnovskaya, Igor L. Nikonov, Anton N. Tsmokalyuk, Grigory A. Kim, Sougata Santra, Dmitry S. Kopchuk, Emiliya V. Nosova, Grigory V. Zyryanov
Summary: In this study, new complexes of Eu(III), Tb(III), Gd(III), and Sm(III) with bipyridine ligands containing TEMPO fragments were synthesized and characterized for their interaction with biogenic thiols. Among all the complexes, the Eu(III) complex showed the most promising luminescence and spin-probe properties for the detection of biogenic thiols. The interaction of the Eu(III) complex with free Cys and GSH in solution was confirmed using EPR and fluorescent titration methods. Furthermore, the practical applicability of the Eu(III)-based probe for monitoring AD in vivo was demonstrated through staining of the brain of mice with amyloidosis and Vero cell cultures supplemented with cysteine-enriched medium, as well as fluorescent titration of BSA.
Article
Chemistry, Multidisciplinary
Margarita. O. O. Tonkushina, Kirill. V. V. Grzhegorzhevskii, Alexander. A. A. Ermoshin, Anastasia. S. S. Tugbaeva, Grigory. A. A. Kim, Olga. S. S. Taniya, Ilya. D. D. Gagarin, Alexander. A. A. Ostroushko
Summary: This article investigates the binding between the antitumor drug doxorubicin (DOX) and the nanocluster polyoxometalate (POM) {Mo72Fe30}, which serves as the drug carrier. The formation of a stoichiometric complex POM@(DOX)(12) in aqueous media is observed. Various spectroscopic techniques reveal the composition of the complex and the role of {Mo3Fe3} host pores on the POM surface in DOX binding. The ability of DOX to intercalate into DNA after binding with {Mo72Fe30} is explored, along with the pH-dependent release of DOX from POM@(DOX)(12) and the reduction of undesired side effects through immobilization on the POM surface.
Review
Biochemistry & Molecular Biology
Grigory V. Zyryanov, Dmitry S. Kopchuk, Igor S. Kovalev, Sougata Santra, Adinath Majee, Brindaban C. Ranu
Summary: Since their discovery in 2008, pillararenes have been widely used in molecular recognition and supramolecular chemistry, as well as in practical applications such as drug delivery systems. Their unique property of accommodating guest molecules reversibly in their rigid cavity has been harnessed in various applications including molecular devices, stimuli-responsive systems, and organic-inorganic hybrid systems. This review focuses on the important progress made in the past decade in using pillararenes for drug delivery systems.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Alexandra E. E. Kopotilova, Tatyana N. N. Moshkina, Emiliya V. V. Nosova, Galina N. N. Lipunova, Ekaterina S. S. Starnovskaya, Dmitry S. S. Kopchuk, Grigory A. A. Kim, Vasiliy S. S. Gaviko, Pavel A. A. Slepukhin, Valery N. N. Charushin
Summary: Amino-[1,1 ']-biphenyl-containing 3-aryl-[1,2,4]triazolo[4,3-c]quinazoline derivatives with fluorescent properties were synthesized and their structures were confirmed by X-ray diffraction. The compounds exhibited non-planar structures with aryl substituents forming pincer-like conformations. The UV/Vis and photoluminescent properties were investigated in different solvents and in solid state, showing broad emission wavelengths and high quantum yields. Solvatochromic properties and aggregation-induced emission enhancement were observed for the substituted triazoloquinazolines. Moreover, changes in absorption and emission spectra were induced by trifluoroacetic acid and acidochromism was observed for some triazoloquinazoline compounds. Electronic-structure calculations were performed for the synthesized compounds.
Review
Polymer Science
Wahab K. A. Al-Ithawi, Albert F. Khasanov, Igor S. Kovalev, Igor L. Nikonov, Vadim A. Platonov, Dmitry S. Kopchuk, Sougata Santra, Grigory V. Zyryanov, Brindaban C. Ranu
Summary: Mechanochemically induced methods are commonly used for polymer depolymerization, but rarely used for polymer synthesis. Mechanochemical polymerization offers advantages such as less solvent consumption, accessibility of novel structures, inclusion of co-polymers and post-modified polymers, and avoidance of problems caused by low monomer solubility and fast precipitation. The development of new functional polymers and materials, including those based on mechanochemically synthesized polymers, has drawn much interest, particularly from the perspective of green chemistry. This review highlights representative examples of transition-metal-free and transition-metal-catalyzed mechanosynthesis of functional polymers.
Article
Chemistry, Inorganic & Nuclear
Andrey Denikaev, Grigory Kim, Evgeny Greshnyakov, Nikolai Moskalenko, Kirill Grzhegorzhevskii
Summary: The study demonstrates a novel synthetic approach for covalently grafting the xanthene dye eosin Y (EY) to the nanoscale Keplerate POM {Mo-132} via an organosilicon linker. This method allows for precise control of the stoichiometry in the POM-dye conjugates and can be applied to graft various organic dyes or molecules to the POM surface in a variety of organic solvents.
Article
Chemistry, Multidisciplinary
Wahab K. A. Al-Ithawi, Albert F. Khasanov, Igor S. Kovalev, Igor L. Nikonov, Dmitry S. Kopchuk, Vadim A. Platonov, Sougata Santra, Grigory V. Zyryanov, Brindaban C. Ranu
Summary: The mechanosynthesis of simple Schiff's bases-based probes S1-S3 for visual detection of CN- anion is reported. These probes were obtained by reacting isomeric 4,4-, 3,3- and 2,2-diaminobiphenyls with 4-nitrobenzaldehyde under ball milling conditions. The probes showed high selectivity and sensitivity toward CN- anion through a dramatic color change, with detection limits in the ppm range.
CHEMISTRY-SWITZERLAND
(2023)
Review
Chemistry, Physical
Olga S. Taniya, Albert F. Khasanov, Leila K. Sadieva, Sougata Santra, Igor L. Nikonov, Wahab K. A. Al-Ithawi, Igor S. Kovalev, Dmitry S. Kopchuk, Grigory V. Zyryanov, Brindaban C. Ranu
Summary: In recent times, there has been a high demand for remote detection methods of warfare agents and explosives. Among these methods, fluorescence methods are more convenient due to their low cost, simplicity, fast response time, and visual sensory response. This review focuses on the use of polymers and polymer-based materials for the detection of nitroaromatic compounds (NACs) and nitro-explosives (NEs) in the past decade. The study highlights the various sensing mechanisms and amplification of sensory response achieved by fluorescent (bio)polymers and (bio)polymer-based materials.
Article
Polymer Science
Wahab K. A. Al-Ithawi, Rammohan Aluru, Artem V. Baklykov, Albert F. Khasanov, Igor S. Kovalev, Igor L. Nikonov, Dmitry S. Kopchuk, Alexander S. Novikov, Sougata Santra, Grigory V. Zyryanov, Brindaban C. Ranu
Summary: This manuscript reports the first mechanochemical approach towards aromatic PUs via reactions between isomeric 2,2'-, 3,3'-, and 4,4'-diaminobiphenyls and triphosgene under solvent-free conditions following ball-milling. Both PUs and azomethine-capped PUs were obtained using this synthetic approach. The fluorescence response of these PUs towards various anions in solutions were studied, showing selective fluorescence responses towards hydroxyl and fluoride anions.
Article
Biochemistry & Molecular Biology
Mohammed S. Mohammed, Igor S. Kovalev, Natalya V. Slovesnova, Leila K. Sadieva, Vadim A. Platonov, Grigory A. Kim, Rammohan Aluru, Alexander S. Novikov, Olga S. Taniya, Valery N. Charushin
Summary: Two new azaheterocycle-based bolas, namely (1-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl)-1H-1,2,3-triazol-4-yl)-methylenyls and alpha,omega-bisfunctionalized PEGs, were synthesized through Cu-catalyzed click reaction. These bola molecules, with two heteroaromatic cores and a PEG linker, are considered as potential fluorescent chemosensors for electron-deficient species. The experimental results showed a significant fluorescence turn-off response towards commonly used nitro-explosive components, such as 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT), as well as hard-to-detect pentaerythritol tetranitrate (PETN) and Hg2+ cation.
Article
Biochemistry & Molecular Biology
Mohammed S. Mohammed, Igor S. Kovalev, Natalya V. Slovesnova, Leila K. Sadieva, Vadim A. Platonov, Alexander S. Novikov, Sougata Santra, Julia E. Morozova, Grigory V. Zyryanov, Valery N. Charushin, Brindaban C. Ranu
Summary: This manuscript reports the synthesis of 2-Ar-5-(4-(4-Ar'-1H-1,2,3-triazol-1-yl)phenyl)-1,3,4-oxadiazoles as PAH-based aza-analogues of POPOP by Cu-catalyzed click reaction. The photophysical properties of the obtained products were investigated, and their sensory response to nitroanalytes was evaluated. Dramatic fluorescence quenching by nitroanalytes was observed in the case of pyrenyl-1-substituted aza-POPOP.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Kirill Grzhegorzhevskii, Ekaterina Rudakova, Alexey Krinochkin, Dmitry Kopchuk, Yaroslav Shtaitz, Lidia Adamova, Grigory Kim, Elena Rusinova, Alisa Shmidt
Summary: This study presents a method to create biocompatible hydrogels with pH-dependent release of loaded molecules using the properties of polyoxometalate. By forming a semi-interpenetrating polymer network through molecular complementarity, the hydrogel exhibits self-healing and pH-sensitive response. The study also evaluates the release of a fluorescent tag using the hydrogel system, showing promising potential for drug-delivery applications.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
A. P. Krinochkin, Ya K. Shtaitz, M. Savchuk, D. S. Kopchuk, N. Slovesnova, I. S. Kovalev, E. Nosova, G. Zyryanov, O. N. Chupakhin
Summary: An efficient method has been developed for synthesizing 2-phenyl-1,3,4-oxadiazole derivatives with one or two pyrrolidin-1-yl substituents in the benzene ring. This is achieved through nucleophilic substitution of fluorine in 2-[(di)fluorophenyl]-1,3,4-oxadiazole by heating with pyrrolidine under solvent-free conditions.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
