Article
Chemistry, Multidisciplinary
Nataliya N. Makhmudiyarova, Irina R. Ishmukhametova, Kamil R. Shangaraev, Lilya U. Dzhemileva, Vladimir A. D'yakonov, Askhat G. Ibragimov, Usein M. Dzhemilev
Summary: An efficient method for synthesizing benzannelated macrocyclic di- and triperoxides has been developed, and it has been demonstrated for the first time using flow cytometry that these compounds are efficient apoptosis inducers in tumor cell cultures and fibroblasts.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Niklas Aders, Jan-Hendrik Lamm, Katharina Wels, Sophie Bernhardt, Beate Neumann, Hans-Georg Stammler, Norbert W. Mitzel
Summary: In this study, highly rigid cyclic and bicyclic compounds containing silicon and tin were synthesized using di-lithiated diethynylbenzene derivatives. The known precursor compounds were efficiently synthesized in a two-step one-pot reaction, resulting in yields up to 45% by alternating addition of the lithiation reagent and starting material. A total of ten compounds were synthesized, with the molecular structure in the solid state elucidated for six novel compounds. Host-guest experiments were conducted to investigate the potential of complexation of small anions using selected molecules. All compounds were characterized using various analytical techniques.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shuai Liu, Lu Zhang, Liang Xu, Pin Gao, Xin-Hua Duan, Li-Na Guo
Summary: This study describes a concise Fe-catalyzed alkylazidation of alpha-trifluormethylalkenes via a C-C bond cleavage/radical addition/azidation cascade. The protocol offers a practical and step-economic approach to the synthesis of tertiary alpha-trifluoromethyl azides, with broad substrate scope, excellent functional group compatibility, and the ability to be performed on a gram scale.
Article
Agriculture, Multidisciplinary
Liu Xu, Xiaocao Quan, Zhong Li, Peter Maienfisch
Summary: We conducted a research program to discover novel ethylsulfonylpyridines as insecticides with a broader spectrum, wider range of uses, and/or improved properties by introducing silicon motifs and studying their biological effects. We designed a series of Oxazosulfyl analogues in which the hydrogen atom at the 5-position of the pyridyl moiety is replaced by a trialkylsilyl group and prepared these compounds using denovo synthetic methodology. Our novel ethylsulfonylpyridines exhibited excellent insecticidal activities, with the best compound, A18, reaching the activity level of the commercial standard Oxazosulfyl against Plutella xylostella.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Jiayou Cai, Bin Sun, Siqi Yu, Han Zhang, Weicheng Zhang
Summary: The review provides a systematic account of the intramolecular Heck reaction in synthesizing non-natural macrocycles. It highlights the importance of this reaction in forming synthetic macrocycles, particularly macrocyclic drugs, beyond the realm of natural product synthesis. The review covers two sections, drug discovery research and synthetic methodology development, to demonstrate the versatile role of Heck macrocyclization.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Leping Wei, Xin Deng, Xiaohui Yu, Xiaohui Li, Wei Wang, Chunfang Zhang, Jinchong Xiao
Summary: Two novel double pi-extended [n]helicene (n = 5, 6) derivatives including pentagonal rings were synthesized and characterized, and their crystal structures revealed offset packing models. Optical resolution was performed on one compound, followed by the examination of their chiroptical properties and DFT calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Reka Mokrai, Anabella Mocanu, Matthew P. Duffy, Thomas Vives, Elsa Caytan, Vincent Dorcet, Thierry Roisnel, Laszlo Nyulaszi, Zoltan Benko, Pierre-Antoine Bouit, Muriel Hissler
Summary: The stereospecific synthesis of helicenoid-based phosphepines and chiral P-containing polycyclic aromatic hydrocarbons is presented, with investigation into the impact of molecular design on structure, (chir)optical properties (including circularly polarized luminescence), and redox properties. An axial to central chirality transfer from the BINAP moiety to the P-atom is observed in these systems.
CHEMICAL COMMUNICATIONS
(2021)
Review
Materials Science, Multidisciplinary
Fangyuan Kang, Jie Yang, Qichun Zhang
Summary: Azaacenes are an important class of organic materials and have made significant progress in terms of synthesis and applications as organic semiconductors in recent years. In addition to the common method of using sterically-shielding substituents to stabilize larger azaacenes, another approach of inserting nonbenzenoid rings has also been developed to achieve stabilization and enlargement, as well as to tune their optical and electronic properties.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Duy T. M. Chung, Phuong Vy Tran, Khiem Chau Nguyen, Pengzhi Wang, Jonathan S. Lindsey
Summary: A new route for synthesizing bacteriochlorophyll a and analogues was explored in this study, revealing the impact of different substituents on synthetic steps and yields. The results also highlight obstacles and opportunities in the total synthesis of native pigments.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yunkai Sun, Yaqian Ding, Wenwen Zhou, Xiaofeng Wang, Chunhong Tan, Yoshimasa Matsumura, Bungo Ochiai, Quanli Chu
Summary: The polymers polyBAUEE and polyBAUP exhibit high selectivity and efficiency in adsorbing precious metal ions, with polyBAUEE showing faster adsorption rates and higher adsorption capacities compared to polyBAUP. Additionally, the adsorption process results in the reduction of Au(III) to Au(0) nanoparticles, indicating a regioselective recognition mechanism based on the ring structure and ureido groups.
Article
Chemistry, Physical
Yuwei Chen, Yidong Liu, Yonggang Min
Summary: Recent studies have shown that the introduction of silicon can effectively improve the dielectric properties of polyimide (PI) and increase the flexibility of the PI molecular structure by introducing a silicon-oxygen bond, which helps reduce the moisture absorption rate of PI materials. In this experiment, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl disiloxane (DSX) was mixed with 4,4'-diaminodiphenyl ether (ODA) in different proportions. A series of PI films containing silicon were obtained by random and tetrad copolymerization with different dianhydrides. The characterization results were consistent with the simulation, and the best overall PI formula was obtained when the ratio of diamines was 1:9 and mixed with PMDA. The performance data showed that the PI film had a vitrification temperature of about 320 degrees C, T-5 of 551 degrees C, water absorption of 1.56%, dielectric constant (Dk) of 2.35, dielectric loss (Df) of 0.007, tensile strength of 70 MPa, and elongation at break of 10.2%.
Article
Chemistry, Organic
Patrycja Sokolowska, Kajetan Dabrowa, Slawomir Jarosz
Summary: A chiral photoresponsive host 1 was prepared with high yield through Cs2CO3-templated macrocyclization. Upon green light irradiation, Trans-1 transforms into long-lived cis-1 (25 days), with the backward transformation triggered by blue light. Both isomers exhibit a preference for potassium among alkali metal cations, and cis-1 binds cations more strongly than trans-1 (K-cis/K-trans <= 4.1).
Article
Agriculture, Multidisciplinary
Xiaocao Quan, Liu Xu, Zhong Li, Peter Maienfisch
Summary: Silicon-containing compounds are sporadically used in crop protection and drug discovery, and they have been shown to increase biological efficacy, reduce toxicity, improve physicochemical properties, and have a favorable impact on the environment.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Mauro Mato, Allegra Franchino, Cristina Garcia-Morales, Antonio M. Echavarren
Summary: This review provides a comprehensive summary of major advances and discoveries in gold-catalyzed synthesis of highly strained carbocycles, including cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, and their heterocyclic or heterosubstituted analogs, demonstrating the powerful application of homogeneous gold catalysis in constructing small ring compounds.
Article
Agriculture, Multidisciplinary
Cong Zhou, Xin Wang, Xiaocao Quan, Jiagao Cheng, Zhong Li, Peter Maienfisch
Summary: Bioisosteric replacement is a powerful strategy in life science research. The substitution of carbon with silicon has shown positive effects on efficacy and safety properties in pharmaceutical and crop protection research. The application of carbon-silicon substitution has led to the discovery of new silicon-containing analogues with improved acaricidal activity. This review discusses molecular design, synthesis, and structure-activity relationships in carbon-silicon bioisosteric substitution.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2022)
Article
Chemistry, Organic
Alexander O. Terent'ev, Igor B. Krylov, Ilya V. Kuzmin, Oleg O. Segida, Andrey V. Lastovko, Mikhail I. Shevchenko, Gennady I. Nikishin, Alexander O. Terent'ev
Summary: The field of free-radical reagents in organic chemistry has focused on aminoxyl radicals for a long time. Diacetyliminoxyl, a readily synthetically available oxime radical, differs from aminoxyl radicals in structure and reactivity, demonstrating exceptional stability and reactivity when used as a radical reagent in organic synthesis. It has shown selectivity in abstracting hydrogen from activated substrates or functional groups and has proven to be effective in intercepting stabilized and sterically hindered C-radicals that cannot be trapped by typical radical scavengers like TEMPO.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Biochemistry & Molecular Biology
Alexander A. Korlyukov, Adam. I. Stash, Alexander R. Romanenko, Damian Trzybinski, Krzysztof Wozniak, Anna V. Vologzhanina
Summary: The nature and strength of interactions in Lamivudine were studied using crystallography and calculations. The crystal structure and charge density distribution were determined for the drug. The effects of intramolecular and intermolecular interactions were compared, and the energy contributions to crystal and ligand-receptor binding were evaluated.
Article
Chemistry, Organic
Stanislav A. Paveliev, Alexander O. Ustyuzhanin, Igor B. Krylov, Alexander O. Terent'ev
Summary: The title compound was synthesized via visible-light-induced radical denitrogenative trifluoromethylation of the corresponding vinyl azide and Cs2CO3-mediated defluorinative cyclization of the resultant azine. Sodium trifluoromethanesulfinate was used as a precursor of CF3 radicals, while graphitic carbon nitride (g-C3N4) acted as an environmentally friendly, cheap, and efficient heterogeneous photocatalyst. The structure of the synthesized compound was confirmed by H-1, C-13, F-19-NMR, IR spectroscopy, and mass spectrometry.
Article
Chemistry, Organic
Evgenii S. Gorlov, Diana V. Shuingalieva, Alexey I. Ilovaisky, Vera A. Vil', Alexander O. Terent'ev
Summary: We have reported a three-component oxidative reaction for the construction of 2'-acyloxy-1,3-dicarbonyl compounds using alkyl ketene dimer, cyclic diacyl peroxide, and trimethyl orthoformate. This synthesis allows the formation of 2'-functionalized 1,3-dicarbonyl compounds instead of the commonly found 2-functionalized moiety. The reaction was performed between 4-butylidene-3-propyloxetan-2-one and cyclopropyl malonoyl peroxide in the presence of trifluoroacetic acid and trimethyl orthoformate at 120°C for 1 hour. The synthesized compound was characterized using NMR spectroscopy, mass spectrometry, and IR spectroscopy.
Review
Chemistry, Physical
Wen-Jun Xie, Olga M. Mulina, Alexander O. Terent'ev, Liang-Nian He
Summary: Metal-organic frameworks (MOFs) are used for catalysis due to their high surface area and porous structure. They show potential for selective electrocatalytic CO2 reduction reaction (ECO2RR) into formic acid (HCOOH). This review discusses the preparation methods of MOFs as electrocatalysts and their advantages. Various MOFs and their derivatives, including metal nanomaterials, carbon-based nanocomposites, single-atom catalysts, and bimetallic nanocomposites, are highlighted. The diversity and controllable modulation of catalytic performance of MOF-based catalysts are dependent on the building units and reaction conditions. Challenges and future research directions of MOF-based catalysts are proposed.
Article
Chemistry, Physical
Tatiana F. Sheshko, Elizaveta M. Borodina, Liliya V. Yafarova, Ekaterina B. Markova, Tatiana A. Kryuchkova, Alexander G. Cherednichenko, Irina A. Zvereva, Alexander O. Terent'ev
Summary: The effect of strontium substitution in the structure of Gd2SrFe2O7 on the production of light olefins by CO hydrogenation was investigated. The experimental results showed that an increase in Sr2+ content led to higher surface basicity and oxygen diffusion rate, facilitating CO dissociative adsorption and reaction with atomic hydrogen.
Article
Chemistry, Physical
Elena R. Lopat'eva, Igor B. Krylov, Alexander O. Terent'ev
Summary: TiO2 is a promising heterogeneous photoredox catalyst, but it is not easily activated by visible light. This study demonstrates the generation of t-BuOO· radicals from tert-butylhydroperoxide catalyzed using commercially available unmodified TiO2 under visible light. The discovery has the potential for highly selective catalytic reactions in organic synthesis.
Article
Chemistry, Multidisciplinary
Nataliya N. Makhmudiyarova, Irina R. Ishmukhametova, Lilya U. Dzhemileva, Vladimir A. D'yakonov, Alexander O. Terent'ev, Usein M. Dzhemilev
Summary: An efficient method has been developed to synthesize N-aryl-1,2,4-dioxazolidines, N-aryl-tetraoxaspiroalkanes, and N-aryl-hexaoxadispiroalkanes with high cytotoxic activity against tumor cells by cycloaminomethylation of OH acids with 1,3,5-triaryl-1,3,5-triazinanes in the presence of lanthanide catalysts.
Article
Agriculture, Multidisciplinary
Olga M. Mulina, Evgeniya D. Bokova, Mikhail M. Doronin, Alexander O. Terent'ev
Summary: TMTD is a crucial fungicide widely used in agriculture. An advanced method of TMTD production is reported, which utilizes electric current and eliminates the need for chemical oxidant, reducing waste and making it economically and ecologically promising.
ACS AGRICULTURAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Anna Egorova, Martina Richter, Maria Khrenova, Elisabeth Dietrich, Andrey Tsedilin, Elena Kazakova, Alexander Lepioshkin, Birgit Jahn, Vladimir Chernyshev, Michaela Schmidtke, Vadim Makarov
Summary: Influenza infections are often worsened by bacterial infections such as Streptococcus pneumoniae. We discovered a new compound that may be useful in the development of small molecules against influenza. This compound inhibits both viral and bacterial neuraminidases, making it a promising candidate for treating influenza pneumonia complicated by bacterial infections.
Article
Chemistry, Organic
Olga M. Mulina, Mikhail M. Doronin, Liang-Nian He, Alexander O. Terent'ev
Summary: Electrochemical sulfonylation of alkenes using disulfides as starting reagents is demonstrated. This reaction is a rare example of disulfides as S-partners in electrochemical C-S coupling reactions. Previously, only sulfenylation reactions occurred with disulfides, leading to sulfides that required further oxidation to form sulfones. In this newly discovered process, vinyl sulfones are selectively formed. The reaction is carried out in an undivided electrochemical cell with a platinum anode and stainless-steel cathode under constant current conditions using KI as a supporting electrolyte and redox catalyst. Both radical and ionic pathways are proposed to be involved in the formation of the desired products based on control experiments, CV study, and literature data.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Andrey S. Kirillov, Egor A. Semenov, Oleg V. Bityukov, Maria A. Kuznetsova, Valentina N. Demidova, Alexander N. Rogozhin, Alexei P. Glinushkin, Vera A. Vil', Alexander O. Terent'ev
Summary: The introduction of thiocyano groups into organic molecules is crucial for the synthesis of active ingredients and synthetic intermediates. Electrochemical thiocyanation provides a sustainable alternative to traditional methods, with high efficiency observed in the electrochemical thiocyanation of 1,3-dicarbonyl compounds using AcOH as the solvent. The resulting thiocyanated compounds exhibited high antifungal activity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Alexander S. Budnikov, Igor B. Krylov, Andrey V. Lastovko, Roman A. Dolotov, Mikhail I. Shevchenko, Alexander O. Terent'ev
Summary: The intermolecular oxime radical addition to C-C bonds was observed and studied for the first time. The diacetyliminoxyl radical was used as a model radical reagent to study the reactivity of oxime radicals towards unsaturated substrates. It was found that the diacetyliminoxyl radical can react with vinylarenes and conjugated dienes to form radical addition products, while unconjugated alkenes can undergo radical addition or allylic hydrogen substitution. Interestingly, substituted alkenes give high yields of C-O coupling products despite steric hindrance, while unsubstituted alkenes give lower yields. This can be explained by the diacetyliminoxyl radical's ability to attack alkenes with the formation of a C-N bond instead of a C-O bond.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
