Archive for November 30, 2015

Tetrahedron Lett., 2015, 7020-7023

A.D. Lisakova, D.S. Ryabukhin, R.E. Trifonov, V.A. Ostrovskii, A.V. Vasilyev

“Alkylation of 5-substituted NH-tetrazoles by alcohols in the superacid CF3SO3H”

Tetrahedron Lett., 2015, 56, 7020-7023

Reactions of 5-substituted NH-tetrazoles with alcohols in the superacid CF3SO3H have been studied. Both the structure of the tetrazole and the nature of alcohol were found to dramatically influence the selectivity of the reaction and yields of products. Tetrazoles bearing phenyl, electron-donating aryl, or benzyl groups at the 5-position, have been alkylated using various alcohols (including MeOH and EtOH) in CF3SO3H upon heating at 60 °C for 0.3–12 h to afford 2-alkyl-2H-tetrazoles in 30–98% yields.

Spinus 2015, A. Shmyreva

Anna Shmyreva has presented a report “Nuclear magnetic resonance study of Ni nanoparticles” at the conference Spinus 2015. Video report you can find here (language: Ru).

Spinus 2015, A. S. Mazur

Anton Mazur has presented a report “Application of solid state NMR for studying the properties of magnetically ordered materials” at the conference Spinus 2015. Video report you can find here (language: Ru)

Green Chemistry, 2015

K.S. Rodygin, V.P. Ananikov

“An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source”

Green Chemistry, 2015, accepted

Chemical reactions involving high-pressure acetylene are not easily performed in a standard laboratory setup. The risk of explosion and technical difficulties drastically complicate the equipment and greatly increase the cost. In this study, we propose the replacement of acetylene with calcium carbide, which was successfully utilized to synthesize practically useful vinyl thioesters in accordance with a simple and environmentally benign procedure. The reaction proceeded under mild conditions using a standard laboratory setup. The optimized reaction conditions allowed the selective synthesis of the vinyl thioesters in high yields, and the reaction conditions can be scaled up to synthesize grams of sulfides from inexpensive starting materials.

Russ. J. Org. Chem., 2015, 640-643

A.P. Molchanov, E.V. Sirotkina, M.M. Efremova, R.R. Kostikov, A.V. Ivanov, V.S. Shcherbakova

“Regio- and Stereoive Cycloaddition of Nitrones to 1-Vinyl-4,5-dihydro-1Н-benzo[g]indole”

Russ. J. Org. Chem., 2015, 51, 640-643

Nitrones cycloaddition to 1-vinyl-4,5-dihydro-1Н-benzo[g]indole proceeds regio- and steroselectively affording a single diastereomer of 5-(hetaryl-substituted)isoxazolidine.

J. Molec. Struct., 2015, 169-173

I.S. Ignatyev, T.A. Kochina, V.V. Avrorin, V.V. Gurzha, I.M. Fundamensky

“Molecular and crystal structure of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane”

J. Molec. Struct., 2015, 1094, 169-173

The crystal structure of 2-phenyl-2-hydro-6-methyl-1,3-dioxa-6-aza-2-silacyclooctane [HPhSi(OCH2CH2)2NMe – phenylhydrosilocane (I)] is determined by single-crystal X-ray diffraction at 100 K. The unit cell consists of four molecules connected only by Van-der-Waals interactions. Each molecule has an eight-membered heterocycle with a phenyl group in the axial position. The Si⋯N transannular bond has a short (2.206 Å) interatomic distance which exceeds only this distance in ocanes with highly electronegative fluorine substituents at Si. Since there exist experimental data on the occurrence of different conformers of I in the liquid phase, the PES of the molecule was analyzed by DFT B3LYP and MP2 methods with the aug-cc-pVDZ basis set. The energy minimum belongs to the boat–chair conformation with the axial position of the phenyl group. Rotation of the phenyl ring around the SiC bond has a barrier ca. 1 kcal/mol. The conformer with the equatorial position of this group lies 6 kcal/mol higher. Interconversion of this conformers which was observed in experiment proceeds through the chair–chair configuration in which the Si⋯N transannular bond is absent and coordination at silicon is tetrahedral, rather than trigonal bipyramidal one observed in other conformers.

Angew. Chem. Int. Ed., 2015, 1-6

S.N. Britvin, S.A. Kashtanov, M.G. Krzhizhanovskaya, A.A. Gurinov, O.V. Glumov, S. Strekopytov, Yu.L. Kretser, A.N. Zaitsev, N.V. Chukanov, S.V. Krivovichev

“Perovskites with the Framework-Forming Xenon”

Angew. Chem. Int. Ed., 2015, 54, 1-6

The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO6) (M=Ca, Sr, Ba) containing framework-forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner-sharing (XeO6) and (NaO6) octahedra arranged in a three-dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated XeVIII and SiIV exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that XeVIII can be incorporated into hyperbaric frameworks such as MgSiO3 perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas.

Tetrahedron, 2015, 7931-7937

D.V. Kurandina, E.V. Eliseenkov, T.S. Khaibulova, A.A. Petrov, V.P. Boyarskiy

“Copper-catalyzed C-N bond cross-coupling of aryl halides and amines in water in the presence of ligand derived oxalyl dihydrazide: scope and limitation”

Tetrahedron, 2015, 71, 7931-7937


An efficient and convenient method has been developed for the copper-catalyzed C–N bond cross-coupling of aryl bromides with electron-donor substituents and aliphatic amines in water. The new ligand system N-phenyloxalyl bishydrazide/hexane-2,5-dione has been shown to be considerably more efficient in the copper-catalyzed C–N bond cross-coupling reaction as compared to the ligands described in the literature and allowed decreasing of the catalyst amount (up to 2 mol %) to achieve acceptable yields of isolated products (46–84%). Acceptor substituted aryl bromides, aryl bromides with substituents in the ortho-position, and some aryl dichlorides can undergo the C–N cross-coupling under the developed conditions, but their reactivity is lower.

Russ. J. Org. Chem., 2015, 972-981

Yu.B. Koptelov, D.O. Antuganov, A.P. Molchanov, R.R. Kostikov

“Steric Hindrances to the Cycloaddition of (Z)-1-Arylmethylidene-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ides to N-Arylmaleimides”

Russ. J. Org. Chem., 2015, 7, 972-981


Sterically hindered cycloaddition of (Z)-1-arylmethylidene-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ides to 4-mono- and 2,6-disubstituted N-arylmaleimides requires prolonged heating (40–60 h) at ~150–155°C and yields mixtures of diastereoisomeric cycloadducts. The observed diastereoselectivity is determined by both electronic and steric interactions, depending on the nature and position of substituents in the azomethine imine and maleimide. The reactions of (Z)-1-(2,6-dichlorobenzylidene)-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ide with 4-substituted N-arylmaleimides give mainly the corresponding cis adducts as a result of preferential exo attack by the dipolarophile, whereas trans adducts predominate in the cycloaddition of (Z)-1-(4-X-benzylidene)-5,5-dimethyl-3-oxopyrazolidin-1-ium-2-ide and (Z)-1-(2,6-dichlorobenzylidene) -5,5-dimethyl-3-oxopyrazolidin- 1-ium-2-ide to 2,6-disubstituted N-arylmaleimides.

International Natural Sciences Tournament

Турнир естественных наук
IV International Natural Sciences Tournament. Student teams competition in applied science and innovation. A short video report about this event you can find here (language: Ru, 1TVSPB).