Article
Biochemistry & Molecular Biology
Dmitriy D. Karcev, Mariia M. Efremova, Alexander P. Molchanov, Nikolai Rostovskii, Mariya A. Kryukova, Alexander S. Bunev, Dmitry A. Khochenkov
Summary: In this study, new highly functionalized 5-spiroisoxazolidines were synthesized through the 1,3-dipolar cycloaddition reaction, which showed good selectivity. The reversibility of these reactions allows for controlling the diastereoselectivity of cycloaddition. Additionally, the reduction reaction of the obtained adducts provides 1,3-aminoalcohols or spirolactones.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Polymer Science
Jinkang Dou, Lijie Cheng, Bojun Tan, Binghui Duan, Minghui Xu, Bozhou Wang, Ning Liu
Summary: A tritopic nitrile oxide with high stability and reactivity was synthesized and used for metal-free crosslinking of alkenyl-terminated binders. The resulting elastomers showed improved mechanical properties, particularly elongation at break. This method can also be applied to energetic binders, demonstrating versatility.
Article
Chemistry, Multidisciplinary
Tobias Sandmeier, Erick M. Carreira
Summary: The study introduces the enantio- and chemoselective N-allylation of oximes, yielding cyclic nitrones and enantioenriched aliphatic allylic alcohols through intramolecular kinetic resolution. The method stands out for its ability to utilize E/Z-isomeric oxime mixtures convergently and high functional group tolerance, showcasing its synthetic utility with the formal synthesis of (+)-halichlorine.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Muhammad Fahad Jamali, Usha Yadav, Mary Merlin Manjaly Babu, Ruchir Kant, Kishor Mohanan
Summary: Here, we report the generation of a cyanonitrone in situ from diazoacetonitrile and nitrosoarene, and its subsequent [3+2] cycloaddition with oxabicyclic alkenes to form fused tricyclic cyanoisoxazolidines. This method can also be applied to access fused tricyclic trifluoromethylated and phosphonylated isoxazolidines. Interestingly, the reductive ring-opening of cyanoisoxazolidines followed by a spontaneous lactonization produces fused tricyclic amino lactones. Additionally, the N-O bond of the obtained tricyclic trifluoromethylated isoxazolidines can be cleaved to obtain 1,3-amino alcohols.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Stefan Flesch, Peter Voehringer
Summary: The chemical reactivity of nitrile imines is widely used in organic synthesis, but our understanding of their electronic and molecular structures is incomplete, and the photoinduced generation mechanism is unknown.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Guanqun Zhang, Abdullah S. Alshreimi, Laura Alonso, Alan Antar, Hsien-Cheng Yu, Shahidul M. Islam, Laura L. Anderson
Summary: A new method for the synthesis of 1-pyrrolines with high regio- and diastereoselectivity has been explored using N-alkenylnitrones and alkynes, with mechanistic studies providing insight into the balance of steric and electronic effects that control the product preferences. This cascade reaction demonstrates the divergent synthetic utility of the new method through diastereoselective derivatization of the 1-pyrrolines prepared.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Anu Jacob, Peter G. G. Jones, Daniel B. B. Werz
Summary: A new method for synthesizing tetrahydroselenophenes with exocyclic double bonds was reported, which involves the reaction of donor-acceptor cyclopropanes (DACs) with lithium alkynylselenolates in the presence of In(OTf)3. The method has a broad substrate scope and high yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Jian-Bin Lu, Shu-Yuan Liang, Wu-Tao Gui, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: A relay catalytic protocol utilizing pyrrolidine and palladium catalysis has been developed for the asymmetric synthesis of 1,3-diamine derivatives from 3-substituted 1,3-dienes, sulfuric diamide, and aldehydes. This one-pot, three-component reaction offers the advantages of high atom step economy and operational simplicity, providing an efficient and straightforward access to valuable 1,3-diamines containing quaternary and tertiary stereogenic centers with moderate to good enantioselectivity.
Article
Polymer Science
Hiromitsu Sogawa, Chen-Gang Wang, Shunsuke Monjiyama, Yosuke Akae, Toshikazu Takata
Summary: Nitrile N-oxides are useful reagents and crosslinkers for catalyst- and byproduct-free 1,3-dipolar cycloaddition reactions. By introducing bulky substituents, the stability of Nitrile N-oxides can be enhanced while reducing their reactivity. An isolatable aliphatic ditopic Nitrile N-oxide was synthesized for efficient catalyst-free crosslinking of unsaturated bond-containing polymers, with the operating temperature of the reaction lowered compared to previous crosslinkers. Efficient crosslinking of natural rubber (NR) was achieved at 40 degrees C without the formation of byproducts, and polyacrylonitrile and nitrile butadiene rubber can also be used for solvent-free crosslinking reactions.
Article
Polymer Science
Jinkang Dou, Minghui Xu, Bojun Tan, Hongchang Mo, Xianming Lu, Bozhou Wang, Ning Liu
Summary: Nitrile N-oxide-based click ligation is a promising technique for polymer crosslinking due to its catalyst-free and byproduct-free reactions. In this study, methyl groups were introduced to enhance the stability and reactivity of phenyl nitrile N-oxides. Novel aromatic nitrile N-oxides were synthesized and used as efficient reagents for catalyst-free crosslinking of natural rubber, resulting in elastomers with good mechanical properties.
Article
Chemistry, Inorganic & Nuclear
A. Nelyubin, N. A. Selivanov, A. Yu Bykov, I. N. Klyukin, A. S. Kubasov, A. P. Zhdanov, K. Yu Zhizhin, N. T. Kuznetsov
Summary: Methods for direct synthesis of N-borylated amino acids have been developed, utilizing the interaction between free amino acids and nitrile derivatives of closo-decaborate and closo-dodecaborate anions. The products were characterized by multinuclear NMR spectroscopy, IR absorption spectroscopy, and ESI mass spectrometry. The structures of two products were determined by X-ray diffraction.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Maria Sakovich, Daria Sokolova, Ivan Alekseev, Ivan Lentin, Alexander Gorbunov, Maria Malakhova, Ivan Ershov, Rustem Zairov, Ilia Korniltsev, Sergey Podyachev, Stanislav Bezzubov, Vladimir Kovalev, Ivan Vatsouro
Summary: The acylation reaction between magnesium enolates of acetophenones and calixarene-based 1-acylbenzotriazoles was systematically studied, resulting in the synthesis of rarely available cone and 1,3-alternate calix[4]arenes with 1,3-diketone groups. The expandability of this synthetic approach towards multifunctional macrocycles was explored, and the ability of the deprotonated calixarene bis(1,3-diketones) to bind transition metal cations was confirmed.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Tian-Ming Liao, Wen-Jiang Ma, Yu-Ning Gao, Ming Bian, Min Jiang, Jin-Tao Liu, Hui-Yu Chen, Zhen-Jiang Liu
Summary: This study presents two green and facile protocols for the synthesis of polyfluoroalkanesulfinyl or alkylsulfinyl 4-isoxazolines. Various aldehyde and ketone derived nitrones reacted with alpha-alkynyl sulfoxides under catalyst- and solvent-free conditions at room temperature, providing a series of polyfluoroalkanesulfinyl or alkylsulfinyl 4-isoxazolines with high efficiency. The synthesis was further improved to a one-pot process in aqueous medium, eliminating the need for isolating the nitrones. These reactions offer easy and environmentally friendly methods for the preparation of sulfinyl 4-isoxazolines.
Article
Chemistry, Multidisciplinary
Lihua Xie, Yi Li, Shunxi Dong, Xiaoming Feng, Xiaohua Liu
Summary: The study demonstrates that the chiral amide-guanidine-catalyzed reaction can achieve the synthesis of chiral indolin-3-one derivatives with two contiguous tetrasubstituted stereocenters, yielding moderate to good results with high diastereoselectivities and enantioselectivities. A possible working mode was proposed to explain the chiral control of the process.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Zhenjie Qi, Shaozhong Wang
Summary: A copper(II)-catalyzed protocol has been developed for the construction of trans-configured beta-lactams and spirocyclic beta-lactams from oximes and methyl propiolate, with excellent substrate flexibility and diastereoselectivity (up to >99:1 dr). In situ FT-IR mechanistic experiments suggest that ketene species may be involved in the formation of beta-lactams.
Article
Chemistry, Inorganic & Nuclear
E. A. Kravchenko, A. A. Gippius, A. V. Tkachev, S. V. Zhurenko, A. V. Golubev, A. S. Kubasov, N. A. Selivanov, G. A. Buzanov, A. Yu. Bykov, K. Yu. Zhizhin, N. T. Kuznetsov
Summary: In this study, three silver cluster compounds with different silver environments were synthesized and investigated using X-ray diffraction analysis, X-ray phase analysis, and nuclear quadrupole resonance (35Cl NQR). The non-covalent interactions between chlorines and surrounding atoms were identified using 35Cl NQR spectroscopy. The results were compared with XRD results to understand the relationship between atomic nuclei contacts and attraction interactions. Different types of interactions were observed in different compounds.
INORGANICA CHIMICA ACTA
(2023)
Article
Biochemistry & Molecular Biology
Elena A. Malinina, Ivan I. Myshletsov, Grigorii A. Buzanov, Alexey S. Kubasov, Irina V. Kozerozhets, Lyudmila V. Goeva, Svetlana E. Nikiforova, Varvara V. Avdeeva, Konstantin Yu. Zhizhin, Nikolay T. Kuznetsov
Summary: Nanocrystalline cobalt monoboride was synthesized by thermal decomposition of precursors [Co(DMF)(6)][An], where [An] = [B12H12](2-) (1), [trans-B20H18](2-) (2) or [B10Cl10](2-) (3) in an argon atmosphere. Three new salt-like compounds 1-3 were obtained by the reaction of Co(NO3)(2) with (Et3NH)(2)[An]. Characterization of the annealed products 1a-3a revealed the presence of BN and CoB for 1a, a higher CoB:BN ratio for 2a with decreased crystallinity, and only CoB for 3a. TEM analysis showed that 1a and 2a had small particle sizes (10-15 nm) and a normal size distribution, while 3a had large particles (200-350 nm) with a broad distribution.
Article
Chemistry, Inorganic & Nuclear
Mikhail A. A. Kinzhalov, Daniil M. M. Ivanov, Anastasia V. V. Shishkina, Anna A. A. Melekhova, Vitalii V. V. Suslonov, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. A. Bokach
Summary: Crystallization of [CuI(CNXyl)(3)] (1) with I-2 resulted in the formation of a series of (XylNC)Cu-I crystal polyiodides, along with the accumulation of iodine. The compounds [Cu(I-3)(CNXyl)(3)] (2(I) and 2(II)), [Cu(I-3)(CNXyl)(3)]center dot 1/2I(2) (2 center dot 1/2I(2)), and [Cu(CNXyl)(3)](I-5) (3) were studied by X-ray diffractometry. The presence of an I-2?I-3(-) halogen bonded linkage in the structure of 2 center dot 1/2I(2) provides insight into the mechanism for the generation of I-5(-) and I-8(2-) ligands from I-2 and metal-coordinated I-3(-).
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Anton V. V. Rozhkov, Eugene A. A. Katlenok, Margarita V. V. Zhmykhova, Maxim L. L. Kuznetsov, Victor N. N. Khrustalev, Kirill I. I. Tugashov, Nadezhda A. A. Bokach, Vadim Yu. Kukushkin
Summary: This study investigates the properties of platinum(II) complexes and anticrown cocrystals with stacked heteroplanar architectures. The results demonstrate that the spodium bonds between Hg···Pt and Hg···C play a crucial role in controlling the stacking orientation. Heteroplanar stacking enhances the phosphorescence lifetimes and solid-state quantum yield.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Maria V. Kashina, Mikhail A. Kinzhalov, Elena Yu. Tupikina, Vadim Yu. Kukushkin
Summary: Analysis of X-ray crystal structures of newly prepared thiocyanate Pd-II and Pt-II complexes revealed the bifurcated ((M) - (N))…S contacts in which angles M…S=C are close to 180 degrees. The noncovalent interactions of M…S=C=N-M' were categorized as linear (approximately 180 degrees) and bent (angle M…S=C 80-120 degrees). The linear structures were primarily determined by crystal packing effects and orbital interactions, while the bent structures were influenced by electrostatic forces.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Artem V. Semenov, Sergey V. Baykov, Natalia S. Soldatova, Kirill K. Geyl, Daniil M. Ivanov, Antonio Frontera, Vadim P. Boyarskiy, Pavel S. Postnikov, Vadim Yu. Kukushkin
Summary: Five new copper(I) complexes were generated and isolated as a solid via a three-component reaction. These complexes consist of dibenzohalolium cation and 1,2,4-oxadiazolate anion, with simultaneous linkage between the O,O atoms of the anion and the halogen atom. The strong three-center halogen bonding between the oxadiazolate moieties and the dibenzohalolium cation was identified as the main force in stabilizing the copper(I) complexes.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ilya N. N. Klyukin, Anastasia V. V. Kolbunova, Alexander S. S. Novikov, Alexey V. V. Nelyubin, Andrey P. P. Zhdanov, Alexey S. S. Kubasov, Nikita A. A. Selivanov, Alexander Yu. Bykov, Konstantin Yu. Zhizhin, Nikolay T. T. Kuznetsov
Summary: A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5](-) was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11](-) and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5](-). The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)(4)N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5](-) was investigated with the help of density functional theory (DFT) calculations.
Article
Chemistry, Inorganic & Nuclear
Ilya N. Klyukin, Anastasia V. Kolbunova, Alexander S. Novikov, Andrey P. Zhdanov, Konstantin Yu. Zhizhin, Nikolay T. Kuznetsov
Summary: A theoretical modelling was conducted to study the interaction process between a protonated complex of carboxonium derivative [2,6-B10H8O2CCH3*H-fac](0) and acetonitrile molecule CH3CN. As a result, a trisubstituted [B10H7O2CCH3(NCCH3)](0) derivative was formed. This reaction follows an electrophile-induced nucleophilic substitution (EINS) mechanism. The intermediates and transition states of the substitution process were identified, with the key intermediate being a dihydrogen H-2 fragment attached to one boron atom (B(H-2) structure motif). Different positions of the cluster cage were evaluated as potential pathways for the nucleophilic substitution, and it was found that substitution on the B-4 position of the cluster cage was the most energetically favorable, resulting in the formation of the [2,4,6-B10H7O2CCH3(NCCH3)](0) isomer.
Article
Chemistry, Inorganic & Nuclear
Svetlana E. E. Nikiforova, Evgeniy Y. Y. Matveev, Alexey S. S. Kubasov, Alexey V. V. Golubev, Lyudmila V. V. Goeva, Elena A. A. Malinina, Konstantin Y. Y. Zhizhin, Nikolay T. T. Kuznetsov
Summary: In this study, the experimental and theoretical foundations of the complexation process between zinc(II) and cadmium(II) with 2-hydroxido-nonahydrido-closo-decaborate(2-) anion [2-B10H9(OH)](2-) in the presence of azaheterocyclic ligands were investigated. The first examples of mixed-ligand Zn(II) and Cd(II) complexes with [2-B10H9(OH)](2-) coordinated by the metal atom were successfully isolated and characterized. The structures of these complexes were determined using single-crystal X-ray diffraction. Density functional theory calculations provided insights into the bonding nature in these complexes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. A. Katlenok, Dmitry M. M. Kryukov, Alexander E. E. Kurtsevich, Konstantin M. M. Degtyarenko, Rashid R. R. Valiev, Oleg V. V. Levin, Vadim Yu. Kukushkin, Anton V. V. Rozhkov
Summary: Binuclear half-lantern platinum(II) complexes [Pt(pbt)(mu-S boolean AND N)] 2 (pbtH = 2-phenylbenzothiazole, S boolean AND N = benzo[d]-thiazole-2-thiolate Pt1, 6-fluorobenzo[d]thiazole-2-thiolate Pt2, 6-chlorobenzo[d]thiazole-2-thiolate Pt3, 6-bromobenzo[d]thiazole-2-thiolate Pt4, and 6-iodobenzo[d]thiazole-2-thiolate Pt5) were synthesized with high yield by reacting [Pt(pbt)(NCMe)(2)]NO3 complex with appropriate benzo[d]thiazole-2-thiole in the presence of tBuOK. Complexes Pt1-5 exhibit intense red photoluminescence with high quantum yields. The substitution of H-to-F and H-to-Cl leads to significantly higher electroluminescence brightness, which is attributed to the intermolecular hydrogen bonding in the F-containing complex Pt2 and Cl-containing complex Pt3.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Amirbek D. Radzhabov, Alyona I. Ledneva, Natalia S. Soldatova, Irina I. Fedorova, Daniil M. Ivanov, Alexey A. Ivanov, Mekhman S. Yusubov, Vadim Yu. Kukushkin, Pavel S. Postnikov
Summary: This study presents the design of 0D, 1D, and 2D supramolecular assemblies based on charge-supported halogen bonds. The addition of carboxylic groups to the aryl ring of benzoic acid enabled the formation of 1D-chained and 2D-layered structures. Theoretical methods, including DFT calculations and electron density analysis, were utilized to confirm the existence of the halogen bonds and verify the interaction partners' philicity in the designed solid-state structures.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Elena A. Malinina, Ivan I. Myshletsov, Grigorii A. Buzanov, Irina V. Kozerozhets, Nikolay P. Simonenko, Tatiana L. Simonenko, Svetlana E. Nikiforova, Varvara V. Avdeeva, Konstantin Yu. Zhizhin, Nikolay T. Kuznetsov
Summary: The thermal reduction of copper(II) complexes was studied at 900 degrees C in an argon atmosphere. It was found that annealing resulted in the formation of a boron-containing copper composite with copper(0) nanoparticles. Physicochemical studies confirmed the composition and electrical properties of the annealed products.
Article
Chemistry, Organic
Amirbek D. Radzhabov, Natalia S. Soldatova, Daniil M. Ivanov, Mekhman S. Yusubov, Vadim Yu. Kukushkin, Pavel S. Postnikov
Summary: We have developed an efficient strategy for the synthesis of diarylselenides using iodonium salts as reactants. This method allows the conversion of trimethoxyphenyl-substituted iodonium salts to diarylselenides in a two-step one-pot reaction sequence. The reaction involves the participation of both iodonium aryl groups for diarylation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: By using X-ray crystallography, the cocrystals 1 center dot C6F6, 2 center dot C6F6, and 1 center dot(OFA)(2) were obtained by crystallizing the half-lantern Pt-2(II) complexes with electron-deficient arenes. The structural data revealed the occurrence of π-π stacking between the arenes and metal square-planes. Density functional theory calculations and orbital interaction analysis confirmed the contribution of noncovalent bonding and charge-transfer interaction in the overall stacking forces.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eugene A. Katlenok, Maxim L. Kuznetsov, Anton V. Cherkasov, Dmitry M. Kryukov, Nadezhda A. Bokach, Vadim Yu. Kukushkin
Summary: In this study, it was observed by X-ray crystallography that the Pt-2(II) complexes form crystals with electron-deficient arenes, and it was verified that there is a π-π stacking interaction between the arenes and the metal square-planes. Density functional theory calculations confirmed the contribution of the noncovalent bond between the arenes and Pt(II) in the overall stacking forces. Orbital interaction analysis demonstrated the significance of the charge-transfer interaction between d(z)(2)(Pt) and pi*(C), attributing the C.Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis showed a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.
INORGANIC CHEMISTRY FRONTIERS
(2023)
