Head of the laboratory: Professor, Dr.Sc., Valery N. KALININ

Staff:

Vakhmistrov V.E., Zaitsev A.V., Kas'yanova R.Sh., Koldobsky A.B., Makarenkov A.V., Moiseev S.K., Ol’shevskaya V.A., PetrushkinaE.A., Ponomarev A.B., Rys E.G., Samarskaya A.S., Sandulenko I.V., Cherepanov I.A., ShilovaO.S., Shostakovskii M.V.

Research fields:

• Medicinal Chemistry

• Organometallics and Transition Metal Complexes in Organic Synthesis

• Chemistry of Carboranes

• Meso-ionic compounds

• Transition Metal Complex Catalysis

Recent main publications:

1. A. Kreienbrink, M. B. Sarosi, E. G. Rys, P. Lonnecke, E. Hey-Hawkins. Carbaborane-Substituted 1,2-Diphosphetanes. Angew. Chem. Int. Ed., 50, (20), 4701-4703 (2011).
2. A.B.Koldobskii, E.V.Solodova, I.A.Godovikov, P.V.Verteletskii, V.N.Kalinin. 1-Bromo-2-trifluoroacetylcyclobutenes as novel building blocks for the construction of trifluoromethyl substituted heterocycles. Part 3: Synthesis of trifluoromethylsubstituted pyridines, condensed with cyclobutene moieties. // J. Fluor. Chem., 131, (8), 873-878 (2010).
3. A.B.Koldobskii, N.P.Tsvetkov, E.V.Solodova, P.V.Verteletskii, I.A.Godovikov, V.N.Kalinin. Synthesis of novel β-dialkylamino-α,β-unsaturated trifluoromethyl ketones containing cyclobutene fragment and their reactions with organolithium and Grignard reagents. // Tetrahedron, 66, (19), 3457-3462 (2010).
4. V.A.Ol’shevskaya, A.N.Savchenko, A.V.Zaitsev, E.G.Kononova, P.V.Petrovskii, A.A.Ramonova, V.V.Tatarskiy Jr., M.M.Moisenovich, V.N.Kalinin, A.A.Shtil. Novel Metal Complexes of Boronated Chlorine e₆ for Photodynamic Therapy. // J. Organomet. Chem., 694, 1632-1637 (2009).
5. V.A.Ol’shevskaya, R.G.Nikitina, A.N.Savchenko, M.V.Malshakova, A.M.Vinogradov, G.V.Golovina, D.V.Belykh, A.V.Kutchin, M.A.Kaplan, V.N.Kalinin, V.A.Kuzmin, A.A.Shtil. Novel boronated chlorin e₆-based photosensitizers: Synthesis, binding to albumin and antitumour efficacy. // Bioorg. Med. Chem., 17, 1297-1306 (2009).
6. V.N.Kalinin, S.N.Lebedev, I.A.Cherepanov, I.A.Godovikov, K.A.Lyssenko, E.Hey-Hawkins. 4-Diphenylphosphinosydnone Imines as Bidentate Ligands. // Polyhedron, 28, 2411-2417 (2009).
7. I.A.Cherepanov, S.N.Lebedev, A.S.Samarskaya, I.A.Godovikov,Yu.V.Nelyubina, V.N.Kalinin. 4-Thio derivatives of sydnone imines. // Mendeleev Commun., 19, 322-323 (2009).
8. E.G.Rys, P.Lonnecke, S.Stadlbauer, V.N.Kalinin, E.Hey-Hawkins. Chiral functionalized bisphosphine ligands: Transition metal complexes of 1,2-bis(tert-butylchlorophosphido)-1,2-dicarba-closo-dodecaborane(12). // Polyhedron, 28, 3467-3472 (2009).
9. I.V.Evsikova, S.K.Moiseev, P.V.Petrovskii, V.N.Kalinin. Carbonate derivatives of 14b-hydroxycodeine. // Russ. Chem. Bull., Int. Ed., 57, (8), 1773-1774 (2008), (Engl. Transl.).
10. S.E.Lyubimov, V.A.Davankov, P.V.Petrovskii, E.Hey-Hawkins, A.A.Tyutyunov, E.G.Rys, V.N.Kalinin.  Chiral Carborane-Derived Thiophosphites: New Generation of Ligands for Rh-catalyzed asymmetric hydrogenation. // J. Organometal. Chem., 693, 3689 (2008).
11. S.E.Lyubimov, V.N.Kalinin, A.A.Tyutyunov, V.A.Ol’shevskaya, Yu.V.Dutikova, Chan Seong Cheong, P.V.Petrovskii, A.S.Safronov, V.A.Davankov. Chiral Phosphites Derived from Carboranes: Electronic Effect in Catalytic Asimmetric Hydrogenation. // Chirality, 21, (1), 2-5 (2008).

Recent patents:

1. V.A.Ol’shevskaya, A.V.Zaitsev, N.D.Chkanikov, A.L.Sigan, V.N.Kalinin. Carboranyl Derivatives of Fluorinated Porphyrines and Their Metal Complexes: Photosensibilisative Properties and Preparations. // Rus. Patent No. 2402554.
2. V.A.Ol’shevskaya, A.N.Savchenko, A.V.Zaitsev, V.N.Kalinin, A.A.Shtil, M.A.Kaplan, R.G.Nikitina, A.A.Ramonova, M.M.Moisenovich, I.I.Agapov. Chlorine е₆ 13(1)-N-{2-[N-(closo-Monocarbadodecabora-1-yl)methyl]aminoethyl}-amide-15(2),17(3)-dimethyl Ester Derivatives with Enhances Antitumor Activity. // Rus. Appl. No.  2009115755 (April 27, 2009). Approved: July 06, 2010.

Head of the laboratory: Dr.Sc., Prof., Valery K. Brel

Staff:

Dr. Aleksanyan D.V., Dr. Artyushin O.I., Dr. Baulina T.V., Dr. Bodrin G.V., Dr. Bykhovskaya O.V., Goryunov E.I., Dr. Kalashnikova A.A., Dr.Sc. Kozlov V.A., PhD student Konovalov A.V., Kudryavtsev I.Yu., Matveev S.V., Dr. Matveeva A.G., Morgalyuk V.P., Pasechnik M.P., Dr. Smirnova E.V., PhD student Spiridonov A.A., Dr. Khodak A.A., Dr., Associate Prof. Churusova S.G., Dr. Sharova E.V., Chaadaev A.B.

History of the Laboratory:

The Laboratory of Organophosphorus Compounds (OPC) was included in a pool of laboratories of the Institute of Organic Chemistry, Russian Academy of Sciences, that provide a basis for the foundation in 1954 of the Institute of Organoelement Compounds. The laboratory was headed by Academician Martin I. Kabachnik (1908-1997) since its foundation till 1991. In 1991–2000, the laboratory was headed by Corresponding Member of the RAS, Doctor of Science (Chem.), Professor Tatiana A. Mastryukova (1925-2006).

In 2000–2006, she became the head of the Laboratory of Organothiophosphorus Compounds (OTPC). In 2007–2012, the Laboratory of OTPC was headed by Doctor of Science (Chem.), Professor Irina L. Odinets. From 2000 to 2012, the OPC Laboratory was headed by Corresponding Member of the RAS, Doctor of Science (Chem.) Eduard E. Nifantiev. From 2013 to the present, the reunited Laboratory of OPC is headed by Doctor of Science (Chem.), Professor Valery K. Brel.

Field of Research:

• Design of new types of organophosphorus extractants and sorbents for the separation and concentration of actinides and lanthanides during the processing of high-level nuclear waste.
• Design of new biologically active molecules with specified properties (antimicrobial, antitumor, antiviral, etc.).
• Functionalization of natural compounds with organophosphorus and pharmacophore fragments.
• Coordination chemistry of (thio)organophosphorus compounds.
• Development of methods for solid-phase and mechanochemical synthesis of metal complex compounds.

Grants and Contracts over 2020—2024:

• 2020-2020 Research work СХ.28389 (Sibur) “Structure of halogen-free flame retardant.” Head: Dr.Sc. V.K. Brel.
• 2020-2022 RSF 20-13-00329 “Polytopic phosphorus–nitrogen ligands on 2D and 3D platforms as effective complexing agents.” Head: Dr.Sc. V.K. Brel.
• 2020-2022 RSF 20-73-00282 “Search for new anticancer drugs in the series of Pd(II) pincer complexes with amino acid and phosphorus residues.” Head: Dr. D.V. Aleksanyan.
• 2022-2024 RSF 22-13-00267 “Development of methods for mechanochemical synthesis of metal complex compounds.” Head: Dr.Sc. V.A. Kozlov.
• 2022-2025 РНФ 22-73-10044 RSF 22-73-10044 “Synthesis and antitumor properties of mono- and binuclear palladium complexes based on thiophosphorylated amides.” Head: Dr. D.V. Aleksanyan.
• 2023-2024 RSF 20-13-00329 (extension) “Polytopic phosphorus-nitrogen ligands on 2D and 3D platforms as effective complexing agents.” Head: Dr.Sc. V.K. Brel.

Awards and prizes:

• 2015 L'Oreal UNESCO Award "For Women in Science". Laureate: Aleksanyan D.V.
• 2019 Scholarship of the President of the Russian Federation in 2019-2021 for young scientists and graduate students carrying out promising scientific research and development in priority areas of modernization of the Russian economy. Laureate: Moiseeva A.A. Project title: "Synthesis of hybrid molecules with cytostatic properties."

List of main publications over 2020—2024:

• I.Y. Kudryavtsev, O.V. Bykhovskaya, A.G. Matveeva, T.V. Baulina, M.P. Pasechnik, S.V. Matveev, A.V. Vologzhanina, A.N. Turanov, V.K. Karandashev, V.K. Brel. New tripodal ligand on the triphenylphosphine oxide platform with 1,2,3‑triazole side arms: synthesis, structure, coordination, and extraction properties. Monatsh Chem, 151:1705–1713, 2020.
• V.K. Brel, O.I. Artyushin, R.N. Chuprov-Netochin, S.V. Leonov, M.N. Semenova, V.V. Semenov. Synthesis and biological evaluation of indolylglyoxylamide bisphosphonates, antimitotic microtubule-targeting derivatives of indibulin with improved aqueous solubility. Bioorg Med Chem Lett, 30(23):127635, 2020.
• D.V. Aleksanyan, S.G. Churusova, V.V. Brunova, E.Y. Rybalkina, O.Y. Susova, A.S. Peregudov, Z.S. Klemenkova, G.L. Denisov, V.A. Kozlov. Synthesis, characterization, and cytotoxic activity of N-metallated rhenium(I) pincer complexes with (thio)phosphoryl pendant arms. J Organomet Chem, 926:121498, 2020.
• M.P. Davydova, I.Y. Bagryanskay, I.A. Bauer, M.I. Rakhmanova, V.P. Morgalyuk, V.K. Brel, A.V. Artem’ev. Green- and red-phosphorescent Mn(II) iodide complexes derived from 1,3-bis(diphenylphosphinyl)propane. Polyhedron, 188:114706, 2020.
• M.Y. Petyuk, A.S. Berezin, I.Y. Bagryanskaya, O.I. Artyushin, V.K. Brel, A.V. Artem'ev. A dinuclear Re(I) tricarbonyl complex showing thermochromicluminescence. Inorg Chem Commun, 119:108058, 2020.
• T.V. Baulina, M.P. Pasechnik, I.Y. Kudryavtsev, O.V. Bykhovskaya, G.Y. Sukat, A.F. Smol’yakov, L.V. Anikina, V.K. Brel. Hydrogen bonding in triols on the triphenylphosphine oxide platform in crystal and solution: Effect of linker length. J Mol Struct, 1217:128324, 2020.
• M.P. Davydova, I.A. Bauer, V.K. Brel, M.I. Rakhmanova, I.Y. Bagryanskaya, A.V. Artem'ev. Manganese(II) thiocyanate complexes with bis(phosphine oxide) ligands: synthesis and excitation wavelength-dependent multicolor luminescence. Eur J Inorg Chem, 695–703, 2020.
• A.Y. Dolbin, V.K. Brel, B.N. Tarasevich, V.E. Pushkarev. Low-symmetry A3B type pentachlorocyclotriphosphazene substituted phthalocyanine with improved nonlinear optical properties: Synthesis, spectroscopic and ab initio/(TD)DFT study. Dyes Pigments, 174:108095, 2020.
• A.N. Turanov, V.K. Karandashev, O.I. Artyushin, V.K. Brel. 1,2,4,5-tetra(diphenylphosphinyl)benzene as novel effective extractant for actinides and lantanides. Solv Extr Ion Exch, 38(2):166–179, 2020.
• D.A. Khanin, Y.N. Kononevich, M.N. Temnikov, V.P. Morgalyuk, V.G. Vasil’ev, A.Y. Popov, V.K. Brel, V.S. Papkov, A.M. Muzafarov. New hybrid materials based on cyclophosphazene and polysiloxane precursors: synthesis and properties. Polymer, 186:122011, 2020.
• D.V. Aleksanyan, S.G. Churusova, V.V. Brunova, A.S. Peregudov, A.M. Shakhov, E.Y. Rybalkina, Z.S. Klemenkova, E.G. Kononova, G.L. Denisov, V.A. Kozlov. Mechanochemistry for the synthesis of non-classical N-metalated palladium(II) pincer complexes. Dalton Trans, 50(45):16726–16738, 2021.
• S.G. Churusova, D.V. Aleksanyan, E.Y. Rybalkina, O.Y. Susova, A.S. Peregudov, V.V. Brunova, E.I. Gutsul, Z.S. Klemenkova, Y.V. Nelyubina, V.N. Glushko, V.A. Kozlov. Palladium(II) pincer complexes of functionalized amides with S-modified cysteine and homocysteine residues: cytotoxic activity and different aspects of their biological effect on living cells. Inorg Chem, 60(13):9880–9898, 2021.
• A.G. Matveeva, O.I. Artyushin, M.P. Pasechnik, A.I. Stash, A.V. Vologzhanina, S.V. Matveev, I.A. Godovikov, R.R. Aysin, A.A. Moiseeva, A.N. Turanov, V.K. Karandashev, V.K. Brel. Coordination and extraction properties of 1,2-bis(diphenylphosphoryl)-benzene toward f-block element nitrates: structural, spectroscopic and DFT characterization of the complexes. Polyhedron, 115085, 2021.
• V.K. Brel, A.A. Moiseeva, O.I. Artyushin, L.V. Anikina, Z.S. Klemenkova. Simple methods of modification of daunorubicin on the daunosamine nitrogen atom. Med Chem Res, 30(3):564–573, 2021.
• A.V. Artem’ev, M.P. Davydova, A.S. Berezin, D.G. Samsonenko, I.Y. Bagryanskaya, V.K. Brel, X. Hei, K.A. Brylev, O.I. Artyushin, L.E. Zelenkov, I.I. Shishkin, L. Jing. New approach toward dual-emissive organic−inorganic hybrids by integrating Mn(II) and Cu(I) emission centers in ionic crystals. ACS Appl Mater Interfaces, 14(27):31000–31009, 2022.
• V.K. Brel, Y.V. Fedorov, A.V. Vologzhanina, P.V. Dorovatovskii. Dinuclear Eu+3 and Tb+3 complexes based on 1,2,4,5-tetrakis(diphenylphosphinyl)-benzene: Synthesis and luminescence properties. Inorg Chem Commun, 146:110181, 2022.
• V.K. Brel, E.P. Alekseychuk, O.I. Artyushin, L.V. Anikina. ”4-alkyl-3-azidomethyl-2-ethoxy-2,5-dihydro-5H-1,2-oxaphosphole 2-oxides: Synthesis and 1,3-cycloaddition”. Synthesis, 54(7):1823–1832, 2022.
• A.G. Matveeva, A.V. Vologzhanina, M.P. Pasechnik, R.R. Aysin, S.V. Matveev, Y.V. Zubavichus, O.I. Artyushin, E.V. Sharova, I.A. Godovikov, V.K. Brel. Competing N vs. P(O),C(O)-coordination in complexes of mono- and bis-1,2,3-triazole ligands modified by carbamoylmethylphosphine oxide fragments with palladium(II), uranyl(II), and lanthanum(III): solid and solution structures. Polyhedron, 115680, 2022.
• A.A. Moiseeva, O.I. Artyushin, L.V. Anikina, Z.S. Klemenkova, V.K. Brel. N-phosphorylation of daunorubicin—synthetic approaches and antiproliferative properties of the products. Med Chem Res, 31(6):1011–1025, 2022.
• M.E. Neganova, E.V. Smirnova, E.V. Sharova, O.I. Artyushin, Y.R. Aleksandrova, E.Y. Yandulova, N.S. Nikolaeva, V.K. Brel. Design of conjugates based on sesquiterpene lactones with polyalkoxybenzenes by “click” chemistry to create potential anticancer agents. Molecules, 27(23):8411, 2022.
• M.E. Neganova, Y.R. Aleksandrov, N.S. Nikolaeva, V.K. Brel. Synthesis and biological testing of 3,5-bis(arylidene)-4-piperidone conjugates with 2,5-dihydro-5H-1,2-oxaphospholenes. Bioorg Med Chem Lett, 74:128940, 2022.
• A.N. Turanov, V.K. Karandashev, O.I. Artyushin, E.V. Sharova. Solvent extraction of lanthanides(III) from nitric acid solutions with novel functionalized ionic liquids based on the carbamoyl(methyl)phosphine oxide pattern in molecular diluents. Solv Extr Ion Exch, 40(3):203–215, 2022.
• D.V. Aleksanyan, S.G. Churusova, E.Y. Rybalkina, Z.S. Klemenkova, G.L. Denisov, V.A. Kozlov. Dinucleating ligands based on functionalized oxalamides: lability of Re(I) coordination with the phosphorus pendant arms. Polyhedron, 218:115742, 2022.
• S.G. Churusova, D.V. Aleksanyan, E.Y. Rybalkina, E.I. Gutsul, A.S. Peregudov, Z.S. Klemenkova, Y.V. Nelyubina, A.G. Buyanovskaya, V.A. Kozlov. Pincer–dipeptide and pseudodipeptide conjugates: synthesis and bioactivity studies. J Inorg Biochem, 235:111908, 2022.
• V.A. Kozlov, D.V. Aleksanyan, S.G. Churusova, A.A. Spiridonov, E.Y. Rybalkina, E.I. Gutsul, S.A. Aksenova, A.A. Korlyukov, A.S. Peregudov, Z.S. Klemenkova. Unsymmetrical Pd(II) pincer complexes with benzothiazole and thiocarbamate flanking units: expedient solvent-free synthesis and anticancer potential. Int J Mol Sci, 24(24):17331, 2023.
• D.V. Aleksanyan, S.G. Churusova, E.V. Dubasova, I.V. Ananyev, O.I. Artyushin, A.S. Peregudov, Z.S. Klemenkova, G.L. Denisov, V.A. Kozlov. Experimental and computational insights into the direct cyclopalladation of different unsymmetrical, yet closely related pincer ligands with thione sulfur donors. Polyhedron, 116303, 2023.
• D.V. Aleksanyan, A.V. Konovalov, S.G. Churusova, E.Y. Rybalkina, A.S. Peregudov, S.A. Aksenova, E.I. Gutsul, Z.S. Klemenkova, V.A. Kozlov. Modulation of the cytotoxic properties of Pd(II) complexes based on functionalized carboxamides featuring labile phosphoryl coordination sites. Pharmaceutics, 15(4):1088, 2023.
• D.V. Aleksanyan, A.A. Spiridonov, S.G. Churusova, E.Y. Rybalkina, A.A. Danshina, A.S. Peregudov, Z.S. Klemenkova, V.A. Kozlov. Thiophosphorylated indoles as a promising platform for the creation of cytotoxic Pd(II) pincer complexes. Inorg Chim Acta, 548:121369, 2023.
• A.V. Konovalov, S.G. Churusova, D.V. Aleksanyan, E.Y. Rybalkina, S.A. Aksenova, A.S. Peregudov, Z.S. Klemenkova, V.A. Kozlov. (Aminoalkyl)diphenylphosphine sulfides: synthesis and application as building blocks in the design of multidentate ligands for cytotoxic Pd(II) complexes. Org Biomol Chem, 2023.
• A.S. Sokolova, O.I. Yarovaya, O.I. Artyushin, E.V. Sharova, D.S. Baev, E.D. Mordvinova, D.N. Shcherbakov, T.A. Shnaider, T.V. Nikitina, I.L. Esaulkova, P.A. Ilyna, V.V. Zarubaev, V.K. Brel, T.G. Tolstikova, N.F. Salakhutdinov. Design, synthesis and antiviral evaluation of novel conjugates of the 1,7,7-trimethylbicyclo[2.2.1]heptane scaffold and saturated N-heterocycles via 1,2,3-triazole linker. Arch Pharm, e2300549, 2023.
• K. Belov, V. Brel, V. Sobornova, I. Fedorova, I. Khodov. Conformational analysis of 1,5-diaryl-3-oxo-1,4-pentadiene derivatives: A nuclear Overhauser effect spectroscopy investigation. Int J Mol Sci, 24:16707, 2023.
• Y.V. Demyanov, Z. Ma, Z. Jia, M.I. Rakhmanova, G.M. Carignan, I.Y. Bagryanskaya, V.S. Sulyaeva, A.A. Globa, V.K. Brel, L. Meng, H. Meng, Q. Lin, L. Jing, A.V. Artemev. Copper(I)-arsine clusters with a near-unity phosphorescence quantum yield for X-ray scintillation and led applications. Adv Opt Mater, 2302904, 2024.

Patents over 2014—2024:

• 2016 Diethyl(3,5-bis(arylidene)-4-oxopiperidin-1-yl)-(aryl)-methylphosphonates with antiproliferative properties. Authors: Klochkov S.G., Brel V.K., Makarov M.V., Anikina L.V., Pukhov S.A. Patent RU No. 2603194, November 27, 2016
• 2018 Method for producing triethylammonium salt of bis(3-aminophenyl)phosphinic acid. Authors: Bondarenko N.A., Tsarkova K.V., Artyushin O.I. Patent RU No. 2659033 C1, June 27, 2018
• 2018 N-Piperonyl derivatives of daunorubicin with antiproliferative properties. Authors: Brel V.K., Artyushin O.I., Sharova E.V., Vinogradova N.M., Moiseeva A.A., Klochkov S.G., Anikina L.V., Genkina G.K. Patent RU No. 2642068, January 24, 2018
• 2019 N-Methoxybenzyl derivatives of daunorubicin with antiproliferative properties. Authors: Artyushin O.I., Moiseeva A.A., Brel V.K., Anikina L.V. Patent RU No. 2704326, October 28, 2019