Ресурсный центр «Магнитно-резонансные методы исследования»

R.O. Iakovenko, A.N. Kazakova, V.M. Muzalevskiy, A.Yu. Ivanov, I.A. Boyarskaya, A. Chicca, V. Petrucci, J. Gertsch, M. Krasavin, G.L. Starova, A.A. Zolotarev, M.S. Avdontceva, V.G. Nenajdenko, A.V. Vasilyev

“Reactions of CF3-enones with arenes under superelectrophilic activation: a pathway to trans-1,3-diaryl-1-CF3-indanes, new cannabinoid receptor ligands”

Org. Biomol. Chem., 2015, 13, 8827-8842

DOI:10.1039/c5ob01072a

4-Aryl-1,1,1-trifluorobut-3-en-2-ones ArCH=CHCOCF₃ (CF₃-enones) react with arenes in excess of Brønsted superacids (TfOH, FSO₃H) to give, stereoselectively, trans-1,3-diaryl-1-trifluoromethyl indanes in 35–85% yields. The reaction intermediates, the O-protonated ArCH=CHC(OH⁺)CF₃ and the O,C-diprotonated ArHC⁺CH₂C(OH⁺)CF₃ species, have been studied by means of ¹H, ¹³C, ¹⁹F NMR, and DFT calculations. Both types of the cations may participate in the reaction, depending on their electrophilicity and electron-donating properties of the arenes. The formation of CF₃-indanes is a result of cascade reaction of protonated CF₃-enones to form chemo-, regio- and stereoselectively three new C–C bonds. The obtained trans-1,3-diaryl-1-trifluoromethyl indanes were investigated as potential ligands for cannabinoid receptors CB₁ and CB₂ types. The most potent compound showed sub-micromolar affinity for both receptor subtypes with a 6-fold selectivity toward the CB2 receptor with no appreciable cytotoxicity toward SHSY5Y cells.

Е.А. Катленок, А.А. Золотарев, А.Ю. Иванов, С.Н. Смирнов, Р.И. Байчурин, К.П. Балашев

“Cтроение, оптические и электрохимические свойства биядерных платинированных комплексов 2-фенилбензотиазола с мостиковыми 2-меркаптопроизводными тиазолина, 1-метилимидазола и пиримидина”

Коорд. Химия, 2015, 41(6), 357-364

DOI:10.7868/S0132344X15060031

Методами РСА и спектроскопии ЯМР 1Н, 13С, 195Pt исследовано строение комплексов [Pt(Bt)(μ(N^S))]2 с платинированным 2-фенилбензотиазолом (Bt) и мостиковыми 2-меркапто производными (N^S) тиазолина, 1-метилимидазола и пиримидина в кристаллическом состоянии и растворе CDCl3. Показано цисN(Bt),S(N^S)строение комплексов [Pt(Bt)(μ(N^S))]2 с химической связью Pt–Pt 2.89–2.93 Å и антисимметричным положением двух циклоплатинированных и двух мостиковых лигандов (CCDC № 1001204 (I), 1027021 (II), 993566 (III)). Длинноволновые полосы поглощения (410–540 нм), полосы фосфоресценции с λ_маx = 685 нм, процессы двух электронного электровосстановления c Ep = –(2.00–2.27) В и окисления c Ep = 0.07–0.20 В отнесены к фото и электростимулированным процессам с участием НСМО и ВЗМО, преимущественно локализованных на π*орбиталях {Pt(Bt)} и σ*орбиталях химической связи металл–металл.

A. Ya. Bespalov, T. L. Gorchakova, A. Yu. Ivanov, M. A. Kuznetsov, L. M. Kuznetsova, A. S. Pankova, L. I. Prokopenko, M. S. Avdontceva

«Alkylation and Aminomethylation of 1,3-Dihydro-2Н-Benzimidazole-2-Thione»

Chem. Heterocycl. Compd, 2015, 50(11), ASAP
DOI: 10.1039/c4ra07840c

Alkylation of 1,3-dihydro-2Н-benzimidazole-2-thione (2-mercapto benzimidazole) with bromoethane and chloroacetic acid derivatives occurrs at the sulfur atom, leading to the corresponding 2-sulfanylbenz-imidazole derivatives. Aminomethylation of 1,3-dihydro-2Н-benzimidazole-2-thione with piperidine and 4-methylpiperidine gives reaction products at both nitrogen atoms, while reaction with morpholine gives derivative at only one nitrogen atom, which is in an equilibrium with the starting compound and bis-adduct in DMSO solution

O.Yu. Bakulina, A.Yu. Ivanov, P.S. Lobanov, D.V. Dar’in

“Synthesis of novel peri-fused heterocyclic systemsdpyrimido [4,5,6-de][1,8]naphthyridines, based on interaction of 4,6-dichloro-2-methylthiopyrimidine-5-carbaldehyde with geminal enediamines”

Tetrahedron , 2014, 70, 7900-7905

DOI:10.1016/j.tet.2014.08.066

The synthetic approach to novel peri-fused heterocyclic systems—pyrimido[4,5,6-de][1,8]naphthyridines, has been developed. It consists of successive treatment of 4,6-dichloro-2-methylthiopyrimidine-5-carbaldehyde with 2 mol of geminal β-(acyl)enediamines and includes substitution of a chlorine atom with the nucleophilic carbon atom of the enediamine and cyclization of the corresponding intermediate.

Поздравляем Александра Юльевича Иванова с новой должностью «ведущего специалиста»!

A. Miroslavov, Y. Polotskii, V. Gurzhiy, A. Ivanov, A. Lumpov, M. Tyupina, G. Sidorenko, P. Tolstoy, D. Maltsev, D. Suglobov

“Technetium and Rhenium Pentacarbonyl Complexes with C2 and C11 ω-Isocyanocarboxylic Acid Esters”

Inorg. Chem. 2014, Article ASAP

Technetium(I) and rhenium(I) pentacarbonyl complexes with ethyl 2-isocyanoacetate and methyl 11-isocyanoundecanoate, [M(CO)₅(CNCH₂COOEt)]ClO₄ (M = Tc (1) and Re (2)) and [M(CO)₅(CN(CH₂)₁₀COOMe)]ClO₄ (M = Tc (3) and Re (4)), were prepared and characterized by IR, ¹H NMR, and ¹³C{¹H} NMR spectroscopy. The crystal structures of 1 and 2 were determined using single-crystal X-ray diffraction. The kinetics of thermal decarbonylation of technetium complexes 1 and 3 in ethylene glycol was studied by IR spectroscopy. The rate constants and activation parameters of this reaction were determined and compared with those for [Tc(CO)₆]⁺. It was found that rhenium complexes 2 and 4 were stable with respect to thermal decarbonylation. Histidine challenge reaction of complexes 1 and 2 in phosphate buffer was examined by IR spectroscopy. In the presence of histidine, the rhenium pentacarbonyl isocyanide complex partially decomposes to form an unidentified yellow precipitate. Technetium analogue 1 is more stable under these conditions.

V.V. Sokolov, A.Yu. Ivanov, M.S. Avdontseva, A.A. Zolotarev

“Stereochemistry and NMR Spectra of Some Tricyclic Condensed Thiazolidine Derivatives with a Bridgehead Nitrogen Atom”

Chem. Hetercycl. Compd. 2014, 50, 550-556

DOI: 10.1007/s10593-014-1506-3

The configuration of a series of tricyclic condensed thiazolidines with a bridgehead nitrogen atom, for which erroneous data had been published, was determined by X-ray structural analysis and NMR spectroscopy.

Специалист РЦ Александр Иванов провел первое из трёх занятий со студентами-магистрантами химического факультета, посвящённое обработке спектров ЯМР.