Center for Magnetic Resonance

A. Stukalov, V.V. Sokolov, V.V. Suslonov, M.A. Kuznetsov

“Pyrazoles and C-Imidoylaziridines through [4+1] Annulation and [2+1] Cycloaddition of 1-Azabuta-1,3-dienes with a Synthetic Equivalent of Phthalimidonitrene”

Eur. J. Org. Chem., 2017, 2587-2595
DOI: 10.1002/ejoc.201700172

Oxidative addition of N-aminophthalimide to 1,2,4-triaryl-1-azabuta-1,3-dienes leads, in most cases, to the regiodefined formation of 1,3,5-triarylpyrazoles in moderate to good yields through [4+1] annulation. This transformation is supposed to proceed by nitrenoid attack onto a lone pair of electrons of the imine nitrogen atom to give the vinylazomethine imine, followed by its 1,5-electrocyclization into pyrazoline and further aromatization into pyrazole. Rare examples of 2-imidoyl-1-phthalimidoaziridines that are formed by competitive [2+1] cycloaddition onto the C=C bond were isolated in low yields for 1-azadienes with electron-deficient aryl substituents at the imine nitrogen atom.

M.A. Kuznetsov, A.N. Shestakov, M. Zibinsky, M. Krasavin, C.T. Supuran, S. Kalinin, Muhammet Tanç

“Synthesis, structure and properties of N-aminosaccharin – A selective inhibitor of human carbonic anhydrase I”

Tetrahedron Lett., 2017, 58, 172-174
DOI:10.1016/j.tetlet.2016.12.005

Previously unknown N-aminosaccharin was prepared in good yield via the one-step direct amination of saccharin sodium salt with hydroxylamine-O-mesitylenesulfonic acid (MSH) and its reactivity investigated. N-aminosaccharin and its derivatives were tested against hCA isoforms and the parent compound was identified to be a selective, low micromolar inhibitor (Ki = 8.8 μM) of hCA I. These findings provide a ligand-efficient starting point for the design of potent hCA I inhibitors – a promising drug target for retinal/cerebral edema treatment.

A.N. Shestakov, A.S. Pankova, P.Golubev, A.F. Khlebnikov, M.A. Kuznetsov

“Brønsted acid mediated cyclizations of ortho-aryl(ethynyl)pyrimidines”

Tetrahedron, 2017, 73, 3939-3948
DOI:10.1016/j.tet.2017.05.070

A high-yielding procedure for the synthesis of 5-aryl-4-(arylethynyl)pyrimidines from easily available 2-aryl-3-hydroxyacrylates is reported. These pyrimidines readily undergo cyclization in strong Brønsted acids and, depending on the substitution in alkynylpyrimidines and the water content of the reaction mixture, yield either benzo[f]quinazolines or derivatives of spiro[cyclohexa-2,5-diene-1,5′-cyclopenta[d]pyrimidin]-4-one. In most cases the cyclization proceeds nearly quantitatively. DFT calculations support the proposed mechanisms induced by the protonation of the triple bond in 5-aryl-4-(arylethynyl)pyrimidines. Fluorescent properties of the obtained heterocycles are also described.

A. Lupachev, E. Abakumov, S. Gubin

“The Influence of Cryogenic Mass Exchange on the Composition and Stabilization Rate of Soil Organic Matter in Cryosols of the Kolyma Lowland (North Yakutia, Russia)”

Geosciences, 2017, 7, 24
DOI:10.3390/geosciences7020024

Soil organic matter (SOM) was studied in different types of organo-mineral material (from surface horizons and partially isolated materials—cryoturbated or buried horizons) sampled from the surface horizons, the central parts of the Cryosol profiles, and the lower active layer. We found that the humic acids (HAs) of the cryoturbated and buried horizons showed an increased degree of oxidation and an increment of alkylaromatic and protonized aromatic fraction content. In contrast, the HAs of the surface horizons showed increased values of alkylic carbon components. The content of free radicals was essentially higher in the surface layers than in the cryoturbated and buried layers. While the bulk soil organic matter composition (total organic carbon, total nitrogen, and aromatic/aliphatic values) was not essentially different between surface, cryoturbated, and buried horizons, there were essential differences in elemental composition, carbon species, and free radical content. This indicates that the degree of humification in cryoturbated and buried organo-mineral material is higher than in surface horizons and that partial isolation results in relative stabilization of such material in soil profiles.