Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
Article
Chemistry, Multidisciplinary
Nils L. Ahlburg, Oliver Hergert, Peter G. Jones, Daniel B. Werz
Summary: A novel class of highly activated donor-acceptor cyclopropanes with a single vinylogous acceptor is presented. These moieties undergo cycloaddition reactions with various substrates to form carbo- and heterocycles. The stereochemical outcome can be controlled by the choice of catalyst. Mechanistic and kinetic experiments were conducted to explain the catalytic cycle and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)
Article
Chemistry, Organic
Prasoon Raj Singh, Pratibha Kalaramna, Shamsad Ali, Avijit Goswami
Summary: A simple protocol has been developed to access thio-/selenopyrrolines through a (3+2)-cycloaddition reaction using SnCl4 as a Lewis acid catalyst. Good chemoselectivity was observed when DACs were treated, indicating that thiocyanate is more reactive than nitrile moiety in such reactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Vincent Pirenne, Emma G. L. Robert, Jerome Waser
Summary: Efficient catalytic activation of donor-acceptor aminocyclopropanes lacking the commonly used diester acceptor was achieved in a (3 + 2) dearomative annulation with indoles, yielding cycloadducts in high yields and high diastereomeric ratios, leading to tricyclic indoline frameworks containing four stereogenic centers.
Article
Chemistry, Organic
Raghuramaiah Mandadapu, Amol Satish Dehade, Shrikant Abhiman Shete, Mark Montgomery, Vikas Sikervar, Ravindra Sonawane
Summary: Two different Lewis acids were utilized to achieve regioselective [3+2] and [3+3] cycloaddition reactions of an azomethine imine with activated cyclopropanes, resulting in moderate yields of tetrahydropyrazolone derivatives and tricyclic tetrahydrofuran derivatives as well as high regioselectivity in forming hexahydropyridazinone derivatives.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Stefano Nicolai, Jerome Waser
Summary: This study reports a Lewis acid catalyzed (4+3) annulative addition reaction for the efficient synthesis of densely substituted azepanes. The reaction achieved good yields and high diastereoselectivity under mild conditions using ytterbium triflate or copper triflate with a trisoxazoline ligand as the catalyst. The obtained cycloadducts were convenient substrates for further modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
David A. McLeod, Mathias Kirk Thogersen, Casper Larsen Barlose, Mette Louise Skipper, Erlaitz Basabe Obregon, Karl Anker Jorgensen
Summary: This study presents a novel enantioselective (8+3) cycloaddition reaction using a chiral bifunctional Bronsted base catalyst. The reaction leverages an anionic activation strategy and differs from typical Lewis-acid activation protocols. Experimental and computational results support the relevance of this reaction and its potential application in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Xinyi Wan, Shan Wang, Chengjun Wu, Jianbo Gan, Cunde Wang
Summary: The synthesis of polysubstituted quinolines was investigated through a Yb(OTf)(3)-mediated annulation of cyclopropane-1,1-dicarbonitriles and 2-aminobenzaldehydes, resulting in generally good yields. The cascade reaction involves ring opening, intermolecular nucleophilic addition, intramolecular nucleophilic addition, and demalononitrile aromatization, with the malononitrile group acting as a removable directing group mediated by Yb(OTf)(3).
Article
Chemistry, Multidisciplinary
Yao Xu, Hai-Xiang Gao, Chengkai Pan, Yue Shi, Chi Zhang, Genping Huang, Chao Feng
Summary: By using photoredox catalysis, we have achieved the (3+3) dipolar cycloaddition of nitrones with aryl cyclopropanes. This reaction exhibits excellent regio- and stereoselectivity and can be applied to a variety of aryl cyclopropane substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Yong Xia, Xiaohua Liu, Xiaoming Feng
Summary: The donor-acceptor (D-A) cyclopropanes, due to the synergistic push-pull effect of vicinal electron-donating and electron-withdrawing groups, are recognized as powerful building blocks for generating polyfunctional reactive intermediates. Enantioselective reactions of D-A cyclopropanes provide an efficient approach to enantioenriched acyclic and cyclic compounds. Chiral Lewis/Bronsted acids, transition metals, and organocatalysts have been designed for such transformations, including ring-openings, annulations, and rearrangements.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Meifeng Hou, Jiajun Li, Fucai Rao, Zuliang Chen, Yingjing Wei
Summary: In this study, the construction of N-heterocyclic eight-membered rings using Lu(OTf)(3) as a catalyst is reported. A formal [4+4] cycloaddition reaction of cyclobutane 1,1-diesters with anthranils was used to deliver oxa-bridged eight-membered heterocycles, providing a potential method for building complex azocine compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Yana Lichtenstein, Ivan S. Golovanov, Sema L. Ioffe, Andrey A. Tabolin
Summary: The synthesis of substituted N-silyloxy aziridines through the reaction of silyl nitronates and enol diazo acetates is described. The process involves the in situ transformation of enol diazo acetates into donor acceptor cyclopropenes, their [3+2]-cycloaddition with nitronates, and subsequent rearrangement of fused isoxazolidine intermediates.
Article
Chemistry, Organic
Subaramaniam Thangamalar, Kannupal Srinivasan
Summary: A series of benzo[d]pyrrolo[2,1-b]thiazoles were synthesized by the (3 + 2) annulation reaction of aroyl-substituted donor- acceptor cyclopropanes with benzothiazoles. The reaction, promoted by a substoichiometric amount of Sc(OTf)3, resulted in the formation of dearomatized (3 + 2) adducts, which underwent unexpected decarbethoxylative and dehydrogenative rearomatization to yield fully aromatized products. The presence of an extra aroyl group in the donor-acceptor cyclopropanes is responsible for the unusual reactivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Pavel Yu. Ushakov, Alexey Yu. Sukhorukov, Sema L. Ioffe, Andrey A. Tabolin
Summary: The Suzuki-Miyaura cross-coupling reaction was suggested as the final C-C bond forming step in a convenient diastereoselective route to trisubstituted isoxazolines, with the synthetic utility of the obtained isoxazolines demonstrated through conversion into valuable products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Vladimir A. Motornov, Andrey A. Tabolin, Sema L. Ioffe
Summary: A facile and versatile method for the synthesis of [5,5]-annulated N-fused heterocycles, pyrrolo[2,1-b]thiazoles and pyrrolo[1,2-b]indazoles, via oxidative [3+2] annulation of nitroalkenes and azolium ylides in the presence of copper(ii) has been developed. The reaction is performed under mild conditions using copper(ii) trifluoroacetate/2,6-lutidine system and gives moderate to good yields of the target N-fused heterocycles. Unique fluorinated derivatives can also be accessed using this methodology with alpha-fluoronitroalkenes.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Yana Lichtenstein, Ivan S. Golovanov, Sema L. Ioffe, Andrey A. Tabolin
Summary: The synthesis of substituted N-silyloxy aziridines through the reaction of silyl nitronates and enol diazo acetates is described. The process involves the in situ transformation of enol diazo acetates into donor acceptor cyclopropenes, their [3+2]-cycloaddition with nitronates, and subsequent rearrangement of fused isoxazolidine intermediates.
Article
Chemistry, Organic
Alexander A. Lukoyanov, Andrey A. Tabolin, Yulia Nelyubina, Sema L. Ioffe, Alexey Yu. Sukhorukov
Summary: It has been discovered that six-membered cyclic nitronates can react with aryne to form a tricyclic nitroso acetal. This reaction involves the selective cleavage of the N-O bond of the isoxazoline ring, leading to the synthesis of compounds with potential synthetic value.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Crystallography
Gleb L. Denisov, Yulia Nelyubina
Summary: This study investigates the co-crystallization of gallic acid with pyridines and their polyaromatic analogue, quinoline, and explores the formation of new crystalline products. The introduction of proton-donating groups in the pyridine compound greatly favors the formation of the acid-pyridine heterosynthon in the co-crystals/salts, instead of the acid-acid homosynthon. This modification has the potential to reduce polymorphism and design new pharmaceuticals and crystalline materials.
Article
Chemistry, Multidisciplinary
Evgeniy Chistyakov, Pavel Yudaev, Yulia Nelyubina
Summary: The synthesized compound was characterized using NMR spectroscopy and mass spectrometry, and the crystal structure was determined by X-ray diffraction study.
Article
Chemistry, Multidisciplinary
Anastasia A. Fadeeva, Sema L. Ioffe, Andrey A. Tabolin
Summary: A convenient method for the preparation of 4,5-disubstituted 3-halo- (chloro-, bromo-) isoxazolines has been developed. Acetyl bromide serves as a reducing agent, successfully converting 3-halosubstituted isoxazoline N-oxides into desired deoxygenated derivatives with high yields. This approach is regioselective and eliminates the need for hazardous phosgene oximes. The obtained products have demonstrated selective transformations.
Article
Chemistry, Inorganic & Nuclear
Igor A. Nikovskiy, Kseniia M. Karnaukh, Dmitry Yu Aleshin, Kirill A. Spiridonov, Anastasia A. Danshina, Yulia Nelyubina, Alexander Polezhaev, Valentin V. Novikov
Summary: Here, we report a new di(hydroxyphenyl)imidazolate ligand with an N2O2 donor set synthesized by a modified Debus-Radziszewski procedure. Its binuclear nickel(II) complexes feature a weak antiferromagnetic interaction and ligand-centered oxidation via the formation of cation radicals. The reported ligand widens the range of building blocks available to molecular magnetism community and provides new ways for designing magnetic materials with switchable properties.
Article
Polymer Science
Vladislav A. Tuskaev, Svetlana Ch Gagieva, Dmitrii A. Kurmaev, Yulia Nelyubina, Petr Primakov, Maria D. Evseeva, Evgenii K. Golubev, Mikhail Buzin, Galina G. Nikiforova, Pavel B. Dzhevakov, Viktor Privalov, Kasim F. Magomedov, Boris M. Bulychev
Summary: By synthesizing new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances, the thermal stability of olefin polymerization precatalysts is increased. These catalysts can be used for the synthesis of high molecular weight UHMWPE in the presence of an activator, and can be processed using the solid-phase method. Additionally, these catalysts can be used for ethylene/1-octene copolymerization.
Article
Polymer Science
Ivan V. V. Nazarov, Danil P. P. Zarezin, Ivan A. A. Solomatov, Anastasya A. A. Danshina, Yulia V. V. Nelyubina, Igor R. R. Ilyasov, Maxim V. V. Bermeshev
Summary: This study successfully prepared a series of new optically active polymers by combining norbornene chemistry with chiral natural terpenes. These polymers exhibit high thermal stability and good film-forming properties, making them suitable for enantioselective membrane separation and chiral stationary phases for chromatography.
Article
Biochemistry & Molecular Biology
Nane A. Avagyan, Pavel S. Lemport, Mariia V. Evsiunina, Petr I. Matveev, Svetlana A. Aksenova, Yulia V. Nelyubina, Alexandr V. Yatsenko, Viktor A. Tafeenko, Vladimir G. Petrov, Yuri A. Ustynyuk, Xihe Bi, Valentine G. Nenajdenko
Summary: Three pyrrolidine-derived phenanthroline diamides were studied as ligands for lutetium trinitrate. The presence of halogen atoms in the structure of phenanthroline ligands has a significant impact on the coordination number of lutetium and the number of solvate water molecules. Fluorinated ligands showed higher efficiency based on the measured stability constants. Complexation with lutetium led to a shift in the F-19 NMR signal. The advantages of chlorinated and fluorinated pyrrolidine diamides in liquid-liquid extraction were demonstrated.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Yulia A. Antonova, Yulia V. Nelyubina, Sema L. Ioffe, Andrey A. Tabolin
Summary: A Rh(II)-catalyzed reaction of cyclic nitronates with vinyl diazoacetates proceeds as an annulation reaction, producing bicyclic unsaturated nitroso acetals. Optimization of reaction conditions revealed the use of Rh(II) octanoate as the preferred catalyst in THF at room temperature, allowing the preparation of target products in good yields and excellent diastereoselectivity. Under basic conditions, these nitroso acetals undergo ring contraction into the corresponding pyrroles, and both transformations can be performed in a one-pot fashion.
Article
Chemistry, Physical
Vladimir B. Kharitonov, Dmitry V. Muratov, Yulia V. Nelyubina, Dmitry A. Loginov
Summary: This study demonstrated the influence of catalyst and alkyne nature on the regioselectivity of rhodium-catalyzed annulation of alkoxy-substituted benzoic acids. X-ray diffraction and DFT calculation data showed that the regioselectivity was determined by both steric and coordination effects of methoxy groups. The findings are believed to be applicable to other C-H activation reactions of methoxy-substituted arene compounds.
Article
Chemistry, Organic
Alexander A. A. Lukoyanov, Andrey A. A. Tabolin, Yulia V. V. Nelyubina, Svetlana A. A. Aksenova, Alexey Yu. Sukhorukov
Summary: The reaction between cyclic nitronates and Kobayashi's aryne precursors leads to the formation of tricyclic benzene-fused nitroso acetals through [3 + 2]-cycloaddition. This process is regio- and stereoselective, yielding cycloadducts with up to four contiguous stereogenic centers. These nitroso acetals can be used as convenient precursors for the synthesis of valuable polysubstituted aminodiols through catalytic hydrogenolysis of the N-O bonds. Furthermore, protic acids cause the unusual fragmentation of the cyclic nitroso acetal moiety, leading to the synthesis of a previously unknown hexahydrobenzo[4,5]isoxazolo[2,3-a]azepine scaffold through heterolytic N-O bond cleavage and Beckmann-type reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Pavel Yu. Ushakov, Ivan S. Golovanov, Sema L. Ioffe, Andrey A. Tabolin
Summary: New annulation reactions involving aliphatic nitro compounds and vinyl sulfonium salts were achieved by controlling the reaction direction through changing the solvent and the base. This method is efficient, tolerant to various functional groups, and easy to implement. The synthetic value of the resulting products was demonstrated through selective reduction, selective C-C bond cleavage, and other transformations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
