Article
Chemistry, Physical
Nina K. Ratmanova, Ivan A. Andreev, Vitaly A. Shcherbinin, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Igor V. Trushkov
Summary: Triple-role thiocyanate-containing protic ionic liquids (PILs) were used as a regenerable solvent, a Bronsted acid catalyst, and a nucleophile source to achieve the ring-opening of 1,3-indanedione-based donor-acceptor cyclopropanes.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Organic
Shiksha Deswal, Avishek Guin, Akkattu T. Biju
Summary: The use of benzotriazoles as nucleophilic triggers in the three-component Yb(OTf)(3)-catalyzed ring-opening 1,3-aminofunctionalization of donor-acceptor (D-A) cyclopropanes is described. The reaction yields 1,3-aminohalogenation products in up to 84% yield when N-halo succinimide (NXS) is used as the third component. Alkyl halides or Michael acceptors as the third components lead to the formation of 3,1-carboaminated products in up to 96% yield in a one-pot operation. Using Selectfluor as the electrophile, the reaction affords 1,3-aminofluorinated products in a 61% yield.
Article
Chemistry, Organic
Bastian L. Springer, Kristina Holzschneider, Fabian Mohr, Stefan F. Kirsch
Summary: A new synthetic route for phenanthro[9,10-d]imidazoles is reported. The target compounds were synthesized through the aminolysis of readily accessible 10,10-diazidophenanthren-9(10H)-one with nucleophilic amines, followed by a self-condensation. X-ray single crystallography was used to determine the molecular structures, and the optical properties of the material were described.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Viktoria A. Ikonnikova, Ekaterina A. Zhigileva, Andrei Kuleshov, Vasilissa V. Shirokova, Mikhail S. Baranov, Andrey A. Mikhaylov
Summary: Donor-acceptor cyclopropanes activated by imidazolones undergo alcohol-assisted ring opening under the co-action of p-toluenesulfonic acid, resulting in the coupling of cyclopropanes and alcohols in a 1,3-fashion with the retention of heterocyclic fragment. Substrates with aromatic donor groups provide the addition products in 75-99% yields as mixtures of two diastereomers.
MENDELEEV COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Huimin Jin, Fan Zhou, Zhenhua Xiang, Lingfeng Chen, Guang Liang, Patrick J. Walsh, Jie Li
Summary: This paper describes a base-promoted net-[3+2] cycloaddition of nitriles and 1-arylpropynes for the synthesis of pyrroles. The developed method provides a convenient access to various 2,5-disubstituted or 2,4,5-trisubstituted pyrroles in yields of 40% to 96% (32 examples). Among methods for the synthesis of pyrroles, the protocol presented here stands out for its convenience and atom-economy.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ru Zhong Zhang, Ru Xue Zhang, Shuang Wang, Cong Xu, Wei Guan, Mang Wang
Summary: In this study, an alternative and scalable cyclization strategy based on NCF3-containing synthons was used to construct N-CF3 azoles. This approach allows for the divergent synthesis of N-trifluoromethylated tetrazoles, imidazoles, and 1,2,3-triazoles using various dipoles. The introduction of CF3 onto the nitrogen of heterocycles provides a direct route to such motifs, overcoming the limitations of traditional methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Ivan A. Andreev, Maksim A. Boichenko, Nina K. Ratmanova, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Igor A. Sedov, Igor Trushkov
Summary: A new method for the synthesis of 4-(dimethylamino)pyridinium azide was reported, which is a stable and non-explosive source of azide ion soluble in organic solvents. In protic ionic liquid media, this reagent serves as a safer alternative to toxic and unstable hydrazoic acid. The synthetic utility of this method was demonstrated using a model reaction, showing its wide range of applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Polymer Science
Alexis Emmerich, Constantin C. Daniliuc, Armido Studer
Summary: The stereospecific ionic ring-opening polymerization of various donor-acceptor cyclopropanes allows for the preparation of chiral polymers, with the potential for diverse applications by adjusting the substituents of the monomers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Koena Ghosh, Subhomoy Das
Summary: Ring-opening transformations of donor-acceptor cyclopropanes (DAC) with carbon-centered nucleophiles have shown remarkable progress in the synthesis of diverse 1,3-bifunctional compounds, leading to successful multistep synthesis of complex target molecules in recent years.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Rajesh R. Zalte, Alexey A. Festa, Pavel Raspertov, Olga A. Storozhenko, Nikita E. Golantsov, Victor B. Rybakov, Alexey V. Varlamov, Leonid G. Voskressensky
Summary: Interactions between N-(propargyl)indole-2-carbonitriles and nitrogen nucleophiles were investigated in this study. It was observed that reactions promoted by LiHMDS produced mixtures of two product types, depending on the initial attack on either carbon-carbon or carbon-nitrogen triple bonds. By performing the reaction at reduced temperature and with catalytic amounts of LiHMDS, only alkyne hydroamination products were obtained. On the other hand, a one-pot reaction involving N-(propargyl)indole-2-carbonitriles, methanol, and LiHMDS followed by the addition of a nitrogen nucleophile allowed for a selective cyclization sequence toward 1-aminopyrazino-[1,2-a]indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Grzegorz Mloston, Mateusz Kowalczyk, Andre U. Augustin, Peter G. Jones, Daniel B. Werz
Summary: The reactivity of donor-acceptor cyclopropanes towards thioketenes was investigated, leading to the formation of exocyclic thioenol ethers in moderate to good yields in a (3+2)-cycloaddition using Sc(OTf)(3) as a Lewis acidic catalyst. Unsymmetrical thioketenes provided E/Z mixtures at the double bond, with the Z isomer being preferred.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Organic
Ani Deepthi, C. B. C. Meenakshy, Maneesh Mohan
Summary: This review discusses the use of donor-acceptor cyclopropanes (DACs) for building heterocycles. The generation of heterocycles from DACs can be achieved through (3+2), (3+3), and (4+3) cycloaddition pathways, as well as nucleophilic ring-opening reactions, intramolecular transformations, and cycloisomerizations with suitable catalysts. The mild reaction conditions and the wide range of starting materials make the DAC route attractive for heterocycle synthesis. The literature covered in this review spans from 2018 to 2023.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Ivan A. Andreev, Nina K. Ratmanova, Andre U. Augustin, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Daniel B. Werz, Igor V. Trushkov
Summary: In this study, a new concept of the triple role of protic ionic liquids with nucleophilic anions was proposed, demonstrating their efficiency in ring-opening reactions of donor-acceptor cyclopropanes. The ability of thiocyanate-based protic ionic liquids to serve as a regenerable solvent, a Bronsted acid for catalysis, and a source of nucleophile was exemplified through various organic transformations under mild metal-free conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Jun-Long Zhan, Lin Zhu, Wei Ren, Bing-Jie Wang, Xin-Ming Zhao, Xin-Ru Zhang, Xin-Yu Zhang, Yao-Qiang Xie
Summary: A feasible and umpolung strategy for synthesizing diverse beta-amino ketones was achieved through TEMPO mediated C-N coupling of cyclopropanols with nitrogen nucleophiles. Mechanism studies showed that enones derived from cyclopropanols are key intermediates and TEMPO plays multiple roles. This protocol offers broad substrate scope, good scalability, and good to excellent yields, providing an alternative approach to the synthesis of structurally important beta-amino ketone scaffolds under metal and additive-free conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ivan D. Sorokin, Oleg I. Gromov, Vladimir I. Pergushov, Dania A. Pomogailo, Mikhail Ya. Mel'nikov
MENDELEEV COMMUNICATIONS
(2018)
Article
Chemistry, Multidisciplinary
Ivan D. Sorokin, Oleg I. Gromov, Vladimir I. Pergushov, Dania A. Pomogailo, Mikhail Ya. Melnikov
MENDELEEV COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Tatyana Shabatina, Olga Vernaya, Vladimir P. Shabatin, Michail Y. Melnikov, Alexandr M. Semenov, Vladimir Lozinsky
APPLIED SCIENCES-BASEL
(2020)
Article
Chemistry, Multidisciplinary
Daria A. Pomogailo, Ivan D. Sorokin, Oleg Gromov, Vladimir Pergushov, Mikhail Ya Melnikov
Summary: The structure and nature of radical cations formed upon irradiation of exo-2,3-norbornene oxide solutions in a CF3CCl3 matrix at 77K have been determined using electron paramagnetic resonance, UV-visible absorption spectroscopy, and quantum chemical calculations. A mechanism has been proposed for the photochemical reactions in this system, involving the transformation of the initially formed ring-open radical cation into a ring-closed C-centered radical cation, followed by photoelimination of H2.
MENDELEEV COMMUNICATIONS
(2021)
Article
Polymer Science
Oleg Gromov, Mikhail O. Kostenko, Alexander Petrunin, Anastasia A. Popova, Olga O. Parenago, Nikita Minaev, Elena N. Golubeva, Mikhail Ya Melnikov
Summary: High-pressure electron paramagnetic resonance (EPR) was used to measure the translational diffusion coefficients of a spin probe in PDLLA and swollen in supercritical CO2. Both macroscopic and microscopic scales methods yielded similar results, showing the uniformity of PDLLA on the nanometer scale and unexpected higher rotational mobility of the spin probe in the polymer.
Article
Polymer Science
Ekaterina M. Zubanova, Sergei Kostjuk, Peter S. Timashev, Yury A. Rochev, Alexander Kokorin, Mikhail Ya Melnikov, Elena N. Golubeva
Summary: The coil to globule transition in poly(N-isopropylacrylamide) aqueous solutions was investigated using CW EPR spectroscopy with TEMPO radical as a guest molecule. By using Cu(II) ions as quencher, individual spectra of TEMPO radicals in polymer globule were obtained, showing inhomogeneities in solutions before globule collapsing. EPR spectra simulations confirmed the formation of molten globules initially, followed by further collapsing and densification of the globules as water molecules were released.
Article
Chemistry, Multidisciplinary
I. D. Sorokin, O. Gromov, V. Pergushov, D. A. Pomogailo, M. Ya Melnikov
Summary: The study determined the nature of radical cations stabilized in irradiated frozen solutions of 2,2-dimethyl- and 2,2,3-trimethyloxirane in Freons using EPR, UV/Vis spectroscopy, and quantum chemistry. It was found that the ring-open radical cations formed upon C-C bond cleavage in the oxirane ring undergo intramolecular hydrogen atom transfer under light, leading to the formation of distonic radical cations.
MOSCOW UNIVERSITY CHEMISTRY BULLETIN
(2021)
Review
Chemistry, Physical
Tatyana Shabatina, Olga Vernaya, Aleksei Shumilkin, Alexander Semenov, Mikhail Melnikov
Summary: The increasing appearance of antibiotic-resistant strains of microorganisms is a pressing modern problem. Nanoparticles offer a potential solution as new antibacterial agents, as they can target pathogenic microorganisms using mechanisms different from antibiotics. These particles possess a wide spectrum of antibacterial activity and can be conjugated with drugs for targeted delivery systems.
Article
Polymer Science
Ekaterina M. Zubanova, Tatiana A. Ivanova, Evgenii A. Ksendzov, Sergei Kostjuk, Peter S. Timashev, Mikhail Ya Melnikov, Elena N. Golubeva
Summary: This study investigated the coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers with different contents of oligolactide groups using EPR spectroscopy. It was found that an increase in oligolactide content leads to the formation of looser globules, allowing for the exchange of probe molecules between the globules and the external solution.
Review
Biochemistry & Molecular Biology
Tatyana I. Shabatina, Olga I. Vernaya, Mikhail Y. Melnikov
Summary: The appearance and increasing number of antibiotic-resistant microorganisms is a global problem. Nanoscale inorganic materials have the potential to combat this issue. This article discusses the mechanisms of microbial resistance to antibiotics, the actions of inorganic nanoparticles on bacterial cells, and the benefits of their combined use with antibacterial drugs. The prospects of using metal and metal oxide nanoparticles in targeted delivery systems for antibacterial compositions are also explored.
Review
Pharmacology & Pharmacy
Tatyana I. Shabatina, Olga I. Vernaya, Nikolay L. Shimanovskiy, Mikhail Ya. Melnikov
Summary: The development of antiviral treatment and anticancer theragnostic agents in recent decades has been closely associated with nanotechnologies, especially inorganic nanoparticles (INPs) made of metal and metal oxides. INPs, with their large specific surface area and high activity, can be easily functionalized for various applications such as targeted drug delivery, magnetic hyperthermia, and plasmonic photothermal therapies. The magnetic properties of iron oxide and ferrite nanoparticles make them ideal for magnetic resonance imaging and targeted cancer therapy. Moreover, gold and silver nanoparticles show promise in plasmonic photothermal and antiviral therapies, respectively.
Article
Chemistry, Multidisciplinary
Ivan D. Sorokin, Oleg Gromov, Vladimir Pergushov, Daria A. Pomogailo, Mikhail Ya Melnikov
Summary: Freon matrices affected the nature of species stabilized upon X-ray irradiation of frozen 1,7-dioxaspiro[5,5]undecane solutions at 77 K, resulting in different products in CF3CCI3 and CFCI3, with the ultimate product being a distonic DOSU radical cation in both matrices.
MENDELEEV COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
M. Ya Melnikov, I. D. Sorokin, O. Gromov, V. Pergushov, D. A. Pomogailo
Summary: The study summarizes the data on the photochemical reactions of radical cations derived from various oxiranes that can be stabilized in Freon matrices at 77K, with the nature of the RCs and their products determined through quantum chemistry, EPR, and low-temperature UV/Vis spectroscopy. It shows that depending on the structure of the precursor molecule, transitions between ring-open and ring-closed forms, deprotonation reactions, and more complex transformations can occur with RCs when exposed to light. Possible explanations for the observed effects are discussed.
MOSCOW UNIVERSITY CHEMISTRY BULLETIN
(2021)
Review
Chemistry, Multidisciplinary
Hamidulla B. Tukhtaev, Ivan D. Sorokin, Mikhail Ya. Melnikov, Ekaterina M. Budynina
MENDELEEV COMMUNICATIONS
(2020)
Article
Nanoscience & Nanotechnology
T. I. Shabatina, O. I. Vernaya, A. V. Nuzhdina, N. D. Zvukova, V. P. Shabatin, A. M. Semenov, V. I. Lozinskii, M. Ya. Mel'nikov
NANOTECHNOLOGIES IN RUSSIA
(2018)
