Публикации

ОКИСЛИТЕЛЬНАЯ ГОМОКОНДЕНСАЦИЯ ПЕРВИЧНЫХ АЛКАНОЛОВ В ВОДЕ И КРОСС-КОНДЕНСАЦИЯ В МЕТАНОЛЕ / Г. И. Никишин, Л. Л. Сокова, А. О. Терентьев, Н. И. Капустина // Известия Академии наук. Серия химическая. — Т. 2015, № 12. — С. 2845–2850.

Ammonium iodide-mediated electrosynthesis of unsymmetrical thiosulfonates from arenesulfonohydrazides and thiols / A. O. Terent’ev, O. M. Mulina, A. I. Ilovaisky et al. // Mendeleev Communications. — 2019. — Vol. 29, no. 1. — P. 80–82. A wide range of unsymmetrical thiosulfonates were synthesized from thiols and sulfonyl hydrazides via electrochemical oxidative S-S bond formation in an experimentally convenient undivided electrochemical cell equipped with graphite anode and stainless steel cathode under high current density applying NH4I both as a redox catalyst and a supporting electrolyte. [ DOI ]

Vil V. A., Terent'ev A. O., Mulina O. M. Bioactive natural and synthetic peroxides for the treatment of helminth and protozoan pathogens: Synthesis and properties // Current Topics in Medicinal Chemistry. — 2019. — Vol. 19, no. 14. — P. 1201–1225. [ DOI ]

Electrochemically induced oxidative s–o coupling: synthesis of sulfonates from sulfonyl hydrazides and n-hydroxyimides or n-hydroxybenzotriazoles / A. O. Terent’ev, O. M. Mulina, V. D. Parshin et al. // Organic and Biomolecular Chemistry. — 2019. — Vol. 17, no. 14. — P. 3482–3488. The process of oxidative S–O coupling under the action of electric current was developed. Aryl, hetaryl and alkyl sulfonyl hydrazides and N-hydroxy compounds (N-hydroxyimides and N-hydroxybenzotriazoles) are applied as starting reagents for the preparation of sulfonates. The reaction is carried out under constant current conditions in an experimentally convenient undivided electrochemical cell equipped with a graphite anode and a stainless steel cathode under a high current density (60 mA cm−2). NH4Br in this process acts as a supporting electrolyte and participates in the oxidation of the starting compounds to form a coupling product. The developed strategy represents a quite atom-efficient approach: one partner loses two nitrogen and three hydrogen atoms, while another one loses only one hydrogen atom. Cyclic voltammetry and the control experiment allowed us to propose possible reaction pathways: generated through anodic oxidation molecular bromine or its higher oxidation state derivatives oxidize the starting compounds to form reactive species, which couple to form the S–O bond. [ DOI ]

Mild nitration of pyrazolin-5-ones by a combination of fe(no3)3 and nano2 : Discovery of a new readily available class of fungicides, 4-nitropyrazolin-5-ones / I. B. Krylov, A. S. Budnikov, E. R. Lopat'eva et al. // Chemistry - A European Journal. — 2019. — Vol. 25, no. 23. — P. 5922–5933.

Modern geoecological transformations in the kerch strait ecosystem / D. Y. Fashchuk, A. S. Terent’ev, S. K. Kovalchuk, N. V. Kucheruk // Herald of the Russian Academy of Sciences. — 2019. — no. 1. — P. 72–77. На основе анализа литературных источников 1934 и 1955 гг., архивных данных полевых гидробио-логических исследований Южного НИИ морского рыбного хозяйства и океанографии (ЮгНИРО, Керчь) 1986 и 1989 гг., результатов совместной российско-украинской бентосной съёмки Керчен¬ского пролива (47 станций), выполненной Институтом географии РАН и ЮгНИРО летом 2010 г., исследованы распределение, структура и динамика донных сообществ макрозообентоса Керчен¬ского пролива. Выявлено, что за последние 75 лет в экосистеме пролива деградировали популя¬ции двустворчатых моллюсков фильтраторов – сестонофагов – и получили развитие популяции полихет – собирателей детритофагов, предпочитающих илистые грунты. Выделены виды донных животных и районы пролива, в которых произошли максимальные изменения. После анализа дина¬мики структуры донных осадков пролива по архивным данным ЮгНИРО и результатам водолазной съёмки Института географии РАН 2008 г. (49 погружений) доказано, что одной из причин установ¬ленных трансформаций стало заиление значительной части дна пролива в результате предыдущей (захоронение грунтов дноуглубления, 1960 – 1990 гг.) и современной (строительство Тузлинской дам¬бы, 2003 г.) хозяйственной деятельности. Поскольку характер зафиксированных трансформаций не позволяет полагать указанные причины единственными, авторы рассматривают разные гипоте¬зы, объясняющие механизм этих изменений. Делается вывод о необходимости дальнейшего иссле-дования геоэкологической динамики экосистемы Керченского пролива, особенно сегодня – после строительства Крымского моста. [ DOI ]

Switching of sulfonylation selectivity by nature of solvent and temperature: the reaction of β-dicarbonyl compounds with sodium sulfinates under the action of iron-based oxidants / O. M. Mulina, D. A. Pirgach, G. I. Nikishin, A. O. Terent’ev // European Journal of Organic Chemistry. — 2019. — Vol. 2019, no. 26. — P. 4179–4188. Selectivity of sulfonylation of β-ketoesters with sodium sulfinates under the action of iron(III) salts as oxidants can be regulated by a type of a solvent and reaction temperature. α-Sulfonyl β-ketoesters are obtained when the process is conducted in THF:H2O solution at 40 oC. The change of the solvent to i-PrOH:H2O and refluxing of a reaction mixture provides α-sulfonyl esters — the products of successive sulfonylation-deacylation. When β-diketones are applied as starting materials, only α-sulfonyl ketones are formed. The reaction pathway includes sulfonylation of dicabonyl compounds under the action of Fe(III) to form α-sulfonylated dicarbonyl compounds, which are then attacked by a solvent as the nucleophile, resulting in the products of successive sulfonylation-deacylation. Participation of the solvent in the reaction pathway determines the products structure. [ DOI ]

Применение циклических пероксидов в качестве фунгицидных средств / П. С. Радулов, Ю. Ю. Белякова, И. А. Ярёменко, А. О. Терентьев // Аграрная наука. — 2019. — Т. 2. — С. 169–171. [ DOI ]

Присоединение n-гидроксифталимида и кислорода воздуха к стиролам с использованием трет-бутилгидропероксида как радикального инициатора / И. Б. Крылов, А. С. Будников, А. В. Ластовко и др. // Известия Академии наук. Серия химическая, издательство Наука (М.). — 2019. — № 7. — С. 1454–1457.

Селективный синтез циклических трипероксидов из 1,1´-дигидропероксиди(циклоалкил)пероксидов и кеталей с использованием sncl4 / П. С. Радулов, Ю. Ю. Белякова, А. А. Демина и др. // Известия Академии наук. Серия химическая. — 2019. — Т. 6. — С. 1289–1292.

Binding of potassium ions inside the access channel at the cytoplasmic side of na+,k+-atpase / V. Y. Vishnyakova, V. Y. Tashkin, A. O. Terentjev et al. // Biochemistry, Supplemental Series A. — 2018. — Vol. 12, no. 4. — P. 344–351. [ DOI ]

Five roads that converge at the cyclic peroxy-criegee intermediates: Bf3-catalyzed synthesis of betta-hydroperoxy- betta-peroxylactones / V. A. Vil’, G. G. dos Passos, M. V. Ekimova et al. // The journal of organic chemistry. — 2018. — Vol. 21, no. 83. — P. 13427–13445.

Interrupted bayer-villiger rearrangement: Building a stereoelectronic trap for the criegee intermediate / V. Vil’, G. G. dos Passos, O. Bityukov et al. // Angewandte Chemie - International Edition. — 2018. — Vol. 57. — P. 3372.

New organic peroxides with valuable properties / A. O. Terent'ev, P. S. Radulov, I. A. Yaremenko et al. // Journal of Chemical Engineering & Process Technology. — 2018. — Vol. 1, no. 1. — P. 40.

Novel peroxides as promising anticancer agents with unexpected depressed antimalarial activity / P. Coghi, I. A. Yaremenko, P. Prommana et al. // ChemMedChem. — 2018. Twenty six peroxides belonging to bridged 1,2,4,5‐tetraoxanes, bridged 1,2,4‐trioxolanes (ozonides), and tricyclic monoperoxides were evaluated for their in vitro antimalarial activity against Plasmodium falciparum (3D7) and for their cytotoxic activities against immortalized human normal fibroblast (CCD19Lu), liver (LO2), and lung (BEAS‐2B) cell lines as well as human liver (HepG2) and lung (A549) cancer‐cell lines. Synthetic ozonides were shown to have the highest cytotoxicity on HepG2 (IC50=0.19–0.59 μm), and some of these compounds selectively targeted liver cancer (selectivity index values for compounds 13 a and 14 a are 20 and 28, respectively) at levels that, in some cases, were higher than those of paclitaxel, artemisinin, and artesunic acid. In contrast some ozonides showed only moderate antimalarial activity against the chloroquine‐sensitive 3D7 strain of P. falciparum (IC50 from 2.76 to 24.2 μm; 12 b, IC50=2.76 μm; 13 a, IC50=20.14 μm; 14 a, IC50=6.32 μm). These results suggest that these derivatives have divergent mechanisms of action against cancer cells and malaria‐infected cells. A cyclic voltammetry study of the peroxides was performed, but most of the compounds did not show direct correlation in oxidative capacity–activity. Our findings offer a new source of antimalarial and anticancer agents through structural modification of peroxide compounds. [ DOI ]

Mulina O. M., Ilovaisky A. I., Terent'ev A. O. Oxidative coupling with s-n bond formation // European Journal of Organic Chemistry. — 2018. — Vol. 2018, no. 34. — P. 4648–4672. [ DOI ]

Ozone-free synthesis of ozonides: Assembling bicyclic structures from 1,5-diketones and hydrogen peroxide / I. A. Yaremenko, G. G. dos Passos, P. S. Radulov et al. // The journal of organic chemistry. — 2018. — Vol. 83, no. 8. — P. 4402–4426. Reactions of 1,5-diketones with H2O2 open an ozone-free approach to ozonides. Bridged ozonides are formed readily at room temperature in the presence of strong Brønsted or Lewis acids such as H2SO4, p-TsOH, HBF4, or BF3·Et2O. The expected bridged tetraoxanes, the products of double H2O2 addition, were not detected. This procedure is readily scalable to produce gram quantities of the ozonides. Bridged ozonides are stable and can be useful as building blocks for bioconjugation and further synthetic transformations. Although less stabilized by anomeric interactions than bis-peroxides, ozonides have an intrinsic advantage of having only one weak O–O bond. The role of the synergetic framework of anomeric effects in bis-peroxides is to overcome this intrinsic disadvantage. As the computational data have shown, this is only possible when all anomeric effects in bis-peroxides are activated to their fullest degree. Consequently, the cyclization selectivity is determined by the length of the bridge between the two carbonyl groups of the diketone. The generally large thermodynamic preference for the formation of cyclic bis-peroxides disappears when 1,5-diketones are used as the bis-cyclization precursors. Stereoelectronic analysis suggests that the reason for the bis-peroxide absence is the selective deactivation of anomeric effects in a [3.2.2]tetraoxanonane skeleton by a structural distortion imposed on the tetraoxacyclohexane subunit by the three-carbon bridge. [ DOI ]

Ozonides as promising anticancer agents / I. A. Yaremenko, A. E. Vilikotskiy, Y. Y. Belyakova et al. // Int. J. Drug Dev & Res. — 2018. — Vol. 10. — P. 44.

Similar nature leads to improved properties: cyclic organosilicon triperoxides as promising curing agents for liquid polysiloxanes / K. V. Deriabin, I. A. Yaremenko, M. V. Chislov et al. // New Journal of Chemistry. — 2018. — Vol. 42, no. 18. — P. 15006–15013. [ DOI ]

Пиргач Д. А., Мулина О. М., ТЕРЕНТЬЕВ А. О. Процессы окислительного c-s кросс-сочетания, катализируемые солями металлов переменной валентности // Успехи в химии и химической технологии. — 2018. — Т. 32, № 5. — С. 54–56.

Екимова М. В., Виль В. А., Терентьев А. О. СИНТЕЗ β-ГИДРОПЕРОКСИ-β-ПЕРОКСОЛАКТОНОВ ИЗ β-КЕТОЭФИРОВ И ПЕРОКСИДА ВОДОРОДА // Успехи в химии и химической технологии. — 2018. — Т. 32, № 5. — С. 29–31.

Связывание ионов калия в канале доступа с цитоплазматической стороны na,k,atp-азы / В. Е. Вишнякова, В. Ю. Ташкин, А. О. Терентьев и др. // Биологические мембраны. — 2018. — Т. 35, № 5. — С. 376–383. Изучено связывание ионов калия в канале с цитоплазматической стороны Na,K,ATP-азы и влияние на него рН и ионов магния. Исследования проводили с помощью разработанного ранее метода измерений малых приращений адмиттанса (емкости и проводимости) бислойной липидной мембраны с адсорбированными не ней фрагментами мембран, содержащих Na,K,ATP-азу. Изменение емкости мембраны с Na,K,ATP-азой при освобождении протонов из связанной формы (Caged-H+) вызванном вспышкой УФ света, в отсутствии ионов магния было скачкообразным. В присутствии этих ионов оно состояло из начального быстрого скачка и медленной релаксации к стационарному значению за время около 1-2 с. Кинетика релаксации емкости зависела от рН и концентрации ионов калия. Зависимость быстрого скачка емкости от концентрации ионов калия соответствовала модели конкурентного связывания ионов натрия или калия с протонами, разработанной нами ранее. Эффект ионов магния можно объяснить тем, что эти ионы связываются в Na,K,ATP-азе и влияют на связывание в ней ионов калия либо из-за изменения конформации белка, либо из-за создания электростатических полей в канале доступа с цитоплазматической стороны. [ DOI ]

Chemiluminescence in decomposition of bridged 1,2,4,5-tetraoxanes catalyzed by ferrocene / D. I. Galimov, D. R. Gazeeva, R. G. Bulgakov, A. O. Terent'ev // Mendeleev Communications. — 2017. — Vol. 27, no. 4. — P. 371–373. [ DOI ]

Cyclic peroxides as promising anticancer agents: in vitro cytotoxicity study of synthetic ozonides and tetraoxanes on human prostate cancer cell lines / I. A. Yaremenko, M. A. Syroeshkin, D. O. Levitsky et al. // Medicinal Chemistry Research. — 2017. — Vol. 26, no. 1. — P. 170–179.

Electrosynthesis of vinyl sulfones from alkenes and sulfonyl hydrazides mediated by ki: Аn electrochemical mechanistic study / A. O. Terent'ev, O. M. Mulina, D. A. Pirgach и др. // Tetrahedron. — 2017. — Т. 73. — С. 6871 –6879. [ DOI ]

One-pot oxidative bromination – esterification of aldehydes to 2-bromoesters using cerium (iv) ammonium nitrate and lithium bromide / G. I. Nikishin, N. I. Kapustina, L. L. Sokova et al. // Tetrahedron Letters. — 2017. — Vol. 58, no. 4. — P. 352–354. [ DOI ]

Organic and hybrid systems: from science to practice / V. P. Ananikov, D. B. Eremin, S. A. Yakukhnov et al. // Mendeleev Communications. — 2017. — Vol. 27. — P. 425–438. [ DOI ]

Peroxides with anthelmintic, antiprotozoal, fungicidal and antiviral bioactivity: Properties, synthesis and reactions / V. A. Vil’, I. A. Yaremenko, A. I. Ilovaisky, A. O. Terent’ev // Molecules. — 2017. — Vol. 22, no. 11. — P. 1881–1881. The biological activity of organic peroxides is usually associated with the antimalarial properties of artemisinin and its derivatives. However, the analysis of published data indicates that organic peroxides exhibit a variety of biological activity, which is still being given insufficient attention. In the present review, we deal with natural, semi-synthetic and synthetic peroxides exhibiting anthelmintic, antiprotozoal, fungicidal, antiviral and other activities that have not been described in detail earlier. The review is mainly concerned with the development of methods for the synthesis of biologically active natural peroxides, as well as its isolation from natural sources and the modification of natural peroxides. In addition, much attention is paid to the substantially cheaper biologically active synthetic peroxides. The present review summarizes 217 publications mainly from 2000 onwards. [ DOI ]

Selective oxidative coupling of 3h-pyrazol-3-ones, isoxazol-5(2h)-ones, pyrazolidine-3,5-diones, and barbituric acids with malonyl peroxides: An effective c-o functionalization / A. O. Terent'ev, V. A. Vil', E. S. Gorlov et al. // ChemistrySelect. — 2017. — Vol. 2, no. 11. — P. 3334–3341. Oxidative functionalization of 3H-pyrazol-3-ones, isoxazol-5(2H)-ones, pyrazolidine-3,5-diones, and barbituric acids by malonyl peroxides results exclusively in C−O coupling products. Traditional hydroxylation, formation of carbonyl groups, or oxidative destruction of the heterocyclic ring are not observed. Under optimized reactions conditions – fluorinated alcohols as activating medium and at room temperature (20 – 25 oC) – the selective C−O coupling proceeds in high yields (up to 94 %). The oxidative insertion into the enolizable C−H bond of the substrate is mechanistically viewed as a nucleophilic attack by the heterocycle onto the electrophilically activated malonyl peroxides. For heterocyclic substrates with an active methylene group - 3H-pyrazol-3-ones, isoxazol-5(2H)-ones, and barbituric acids - both C−H bonds are oxidized to afford double oxidative C−O coupling products in good yields (up to 72 %). [ DOI ]

Selective oxidative coupling of 3h-pyrazol-3-ones, isoxazol-5(2h)-ones, pyrazolidine-3,5-diones, and barbituric acids with malonyl peroxides: An effective c-o functionalization / A. O. Terent’ev, V. A. Vil’, E. S. Gorlov et al. // Chemistry Select. — 2017. — Vol. 2. — P. 3334–3341. [ DOI ]

Selective cross-dehydrogenative c-o coupling of n-hydroxy compounds with pyrazolones. introduction of diacetyliminoxyl radical into practice of organic synthesis / K. Igor, P. Stanislav, S. Boris et al. // Organic Chemistry Frontiers. — 2017. — Vol. 4. — P. 1947–1957. [ DOI ]

Selective cross-dehydrogenative c-o coupling of n-hydroxy compounds with pyrazolones. introduction of the diacetyliminoxyl radical into the practice of organic synthesis / I. B. Krylov, S. A. Paveliev, B. N. Shelimov et al. // Organic Chemistry Frontiers. — 2017. — Vol. 4, no. 10. — P. 1947–1957. [ DOI ]

Silica gel mediated oxidative c–o coupling of β-dicarbonyl compounds with malonyl peroxides in solvent-free conditions / O. V. Bityukov, V. A. Vil’, V. M. Merkulova et al. // Pure and Applied Chemistry. — 2017. For the first time silica gel was observed to activate peroxides in oxidative coupling reactions. Here we report silica gel mediated oxidative C–O coupling of β-dicarbonyl compounds with cyclic diacyl peroxides affording α-acyloxy derivatives with 100% atom efficiency. The highest yields of coupling products were achieved in solvent free conditions. C–O coupling products were prepared in yields up to 86%. [ DOI ]

Spontaneous reaction of malonyl peroxides with methanol / M. A. Lapitskaya, V. A. Vil’, L. L. Vasil’eva et al. // Mendeleev Communications. — 2017. — Vol. 27, no. 3. — P. 243–245. The spontaneous reaction of disubstituted malonyl peroxides (MPOs) with methanol affording monopermalonic acid monomethyl esters is fast (minutes) for lower homologues but is sharply decelerated (days) for the higher ones. Spirocyclopropyl-MPO is an exception in which the nucleophilic opening of the spiroactivated cyclopropane ring leads to 2,4-dimethoxy-2-carboxybutanoic acid. [ DOI ]

Stereoelectronic control in the ozone-free synthesis of ozonides / d. P. Gomes Gabriel, I. A. Yaremenko, P. S. Radulov et al. // Angewandte Chemie - International Edition. — 2017. — Vol. 56, no. 18. — P. 4955–4959. The value of stereoelectronic guidelines is illustrated by the discovery of a convenient, ozone-free synthesis of bridged secondary ozonides from 1,5-dicarbonyl compounds and H2O2. The tetraoxane products generally formed in reactions of carbonyl and dicarbonyl compounds with H2O2 were not detected because the structural distortions imposed on the tetraoxacyclohexane subunit in [3.2.2]tetraoxanonanes by the three-carbon bridge leads to the partial deactivation of anomeric effects. The new procedure is readily scalable to produce gram quantities of the ozonides. This reaction enables the selective preparation of ozonides without the use of ozone. [ DOI ]

Stereoelectronic interactions as a probe for the existence of the intramolecular α-effect / J. Eusebio, P. G. Gabriel dos, O. T. Alexander et al. // Complexes, J. Am. Chem. Soc. — 2017. — Vol. 139, no. 31. — P. 10799–10813. [ DOI ]

Synthetic strategies for peroxide ring construction in artemisinin / V. A. Vil’, I. A. Yaremenko, A. I. Ilovaisky, A. O. Terent’ev // Molecules. — 2017. — Vol. 22, no. 1. — P. 117. [ DOI ]

Веденяпина М. Д., Виль В. А., Терентьев А. О. Электрохимическое поведение фталоилпероксида в водной среде // Известия Академии наук. Серия химическая. — 2017. — № 11. — С. 2044–2047. Методом циклической вольтамперометрии (ЦВА) изучено электрохимическое поведение фталоилпероксида C8H4O4 на дисковом Аu"электроде в водном растворе 0.05 М Na2SO4. Он проявляет высокую активность в катодном восстановлении с образованием на ЦВА кривой необратимого пика при E = –0.81 В. В то же время при анодном окислении C8H4O4 поверхность Au электрода покрывается соединениями, препятствующими его окислению при регистрации повторных циклов. Высказано предположение, что эти соединения являются поверхностными комплексами фталоилпероксида с катионом золота.

Adsorption of benzoyl peroxide on activated carbon / M. D. Vedenyapina, E. D. Strel’tsova, V. A. Vill’, A. O. Terent’ev // Solid Fuel Chemistry. — 2016. — Vol. 50, no. 0. — P. 306–309. [ DOI ]

Alcoholysis of malonyl peroxides to give peracids / M. A. Lapitskaya, V. A. Vil', E. D. Daeva et al. // Mendeleev Communications. — 2016. — Vol. 26, no. 1. — P. 14–15. Potassium acetate catalyzed alcoholysis of spirocycloalkyl malonyl peroxides affords 1-alkoxycarbonylcycloalkane-1-percarboxylic acids which are suitable for epoxidation of olefins. [ DOI ]

Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: an electrochemical mechanistic study / A. O. Terent'ev, O. M. Mulina, D. A. Pirgach et al. // RSC advances. — 2016. — Vol. 6. — P. 93476–93485. [ DOI ]

Difference in alpha-thiocyanation of malonates, beta-oxo esters and beta-diketones with sodium thiocyanate and cerium(iv) ammonium nitrate / A. O. Terent'ev, M. Y. Sharipov, A. P. Glinuskin et al. // Mendeleev Communications. — 2016. — Vol. 26, no. 3. — P. 226–227. beta-Diketones and beta-oxo esters are thiocyanated with the NaSCN/(NH4)(2)Ce(NO3)(6) system or with pre-generated dirhodanogen. Malonates undergo thiocyanation only with the NaSCN/(NH4)(2)Ce(NO3)(6) system. [ DOI ]

Electrochemical synthesis of sulfonamides from arenesulfonohydrazides or sodium p-methylbenzenesulfinate and amines / A. O. Terent’ev, O. M. Mulina, D. A. Pirgach et al. // Mendeleev Communications. — 2016. — Vol. 26. — P. 538–539. [ DOI ]

Kinetics and mechanism of the electrochemical reduction of [1,2-bis(tert-butylperoxy)ethyl]benzene under conditions of the in situ recovery of a platinum surface / M. D. Vedenyapina, M. Y. Sharipov, A. O. Terent'ev, A. M. Skundin // Russian Journal of Physical Chemistry A. — 2016. — Vol. 90, no. 2. — P. 475–478. The behavior of [1,2-bis(tert-butylperoxy)ethyl]benzene (I) on Pt electrode is studied by means of cyclic voltammetry (CVA). A comparison of the electrochemical properties of I and the properties of previously studied bridge-type 1,2,4,5-tetraoxane ((1,4)-1,4-dimethyl-7-(4-methylbenzyl)-2,3,5,6-tetraoxabicyclo[2.2.1]heptane) (II) shows that the biperoxide studied in this work is reduced on a Pt electrode at lower cathodic potentials and is resistant to electrooxidation. [ DOI ]

Lanthanide-catalyzed oxyfunctionalization of 1,3-diketones, acetoacetic esters, and malonates by oxidative c-o coupling with malonyl peroxides / A. O. Terent'ev, V. A. Vil', E. S. Gorlov et al. // Journal of Organic Chemistry. — 2016. — Vol. 81, no. 3. — P. 810–823. The lanthanide-catalyzed oxidative C-O coupling of 1,3-dicarbonyl compounds with diacyl peroxides, specifically the cyclic malonyl peroxides, has been developed. An important feature of this new reaction concerns the advantageous role of the peroxide acting both as oxidant and reagent for C-O coupling. It is shown that lanthanide salts may be used in combination with peroxides for selective oxidative transformations. The vast range of lanthanide salts (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Y) catalyzes oxidative C-O coupling much more efficiently than other used Lewis and Bronsted acids. This oxidative cross-coupling protocol furnishes mono and double C-O coupling products chemo-selectively in high yields with a broad substrate scope. The double C-O coupling products may be hydrolyzed to vicinal tricarbonyl compounds, which are otherwise cumbersome to prepare. Based on the present experimental results, a nucleophilic substitution mechanism is proposed for the C-O coupling process in which the lanthanide metal ion serves as Lewis acid to activate the enol of the 1,3-dicarbonyl substrate. The side reactions-chlorination and hydroxylation of the 1,3-dicarbonyl partners-may be minimized under proper conditions. [ DOI ]

Promising hydrogen peroxide stabilizers for large-scale application: unprecedented effect of aryl alkyl ketones / A. O. Terent'ev, Z. Y. Pastukhova, I. A. Yaremenko et al. // Mendeleev Communications. — 2016. — Vol. 26, no. 4. — P. 329–331. Aryl alkyl ketones with substituents in the aromatic ring taken in an amount from 0.005 to 0.5% efficiently stabilize hydrogen peroxide in an aqueous solution during storage at 22-25 degrees C for 16-24 months. [ DOI ]

Promising hydrogen peroxide stabilizers for large-scale application: unprecedented effect of aryl alkyl ketones / A. O. Terent'ev, Z. Y. Pastukhova, I. A. Yaremenko et al. // Mendeleev Communications. — 2016. — Vol. 26, no. 4. — P. 329–331.

Rearrangements of organic peroxides and related processes / I. A. Yaremenko, V. A. Vil, D. V. Demchuk, A. O. Terent'ev // Beilstein Journal of Organic Chemistry. — 2016. — Vol. 12. — P. 1647–1748. This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O-O-bond cleavage. Detailed information about the Baeyer-Villiger, Criegee, Hock, Komblum-DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately. [ DOI ]

Reduction of organosilicon peroxides: Ring contraction and cyclodimerization / A. V. Arzumanyan, A. O. Terent'ev, R. K. Noyikov et al. // Organometallics. — 2016. — Vol. 35, no. 11. — P. 1667–1673. The reduction of 1,7,8-tetraoxa-3,6-disilonanes is accompanied by the selective transformation of two SiOOC moieties into SiOC moieties, resulting in contraction of the nine-membered ring bis-peroxide to a previously unknown class of seven-membered-ring acetals, 1,6-dioxa-2,5-disilepanes. The reduction of six-membered cyclic peroxide proceeds differently and affords four- and eight-membered rings. As a result, silyl ethers of gem-diols; which do not exist in the free form, are produced. [ DOI ]

Selective transformation of tricyclic peroxides with pronounced antischistosomal activity into 2-hydroxy-1,5-diketones using iron (ii) salts / A. O. Terent'ev, Z. Y. Pastukhova, I. A. Yaremenko et al. // Tetrahedron. — 2016. — Vol. 72, no. 24. — P. 3421–3426. The present work deals with selective transformations of peroxides into organic compounds via the cleavage of the O-O bond using variable valence metals. A selective transformation of tricyclic peroxides promoted by Fe2+ salts was discovered. This selective transformation is unexpected for compounds with structural features which allow diverse decomposition pathways. 2-Hydroxy-1,5-diketones are prepared in yields up to 92% in the reactions of tricyclic peroxides with FeSO4, Fe(ClO4)(2), or FeCl2. This is a new preparative method for the synthesis of 1,5-diketones. 2-Hydroxy-1,5-diketones in CDCl3 at 25 degrees C exist mainly in the open-chain form of the hydroxyketone over the cyclic hemiacetal. The results of this work can be of interest to understand the mechanism of the antiparasitic action of peroxides. (C) 2016 Elsevier Ltd. All rights reserved. [ DOI ]

Transformation of 2-allyl-1,3-diketones to bicyclic compounds containing 1,2-dioxolane and tetrahydrofuran rings using the i-2/h2o2 system / A. T. Zdvizhkov, A. O. Terent'ev, P. S. Radulov et al. // Tetrahedron Letters. — 2016. — Vol. 57, no. 8. — P. 949–952. A one-pot procedure was developed for the assembly of bicyclic compounds containing 1,2-dioxolane and tetrahydrofuran rings based on the reaction of 2-allyl-1,3-diketones with the I-2/H2O2 system. A five-fold molar excess of H2O2 and a twofold excess of I-2 are required for the selective formation of tetrahydrofurodioxoles. The synthesis of these structurally complex molecules is unusual in that it does not produce the expected bridged tetraoxanes, products of the addition of several H2O2 molecules to a carbonyl group, or the products of double bond iodoperoxidation. (C) 2016 Elsevier Ltd. All rights reserved. [ DOI ]

Well-known mediators of selective oxidation with unknown electronic structure: Metal-free generation and epr study of imide-n-oxyl radicals / I. B. Krylov, M. O. Kompanets, K. V. Novikova et al. // The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment & general theory. — 2016. — Vol. 120, no. 1. — P. 68–73. Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl radicals are subclass of unique nitroxyl radicals that proved to be useful catalysts and mediators of selective oxidation and CH-functionalization. An efficient metal-free method was developed for the generation of imide-N-oxyl radicals from N-hydroxyimides at room temperature by the reaction with (diacetoxyiodo)benzene. The method allows for the production of high concentrations of free radicals and provides high resolution of their EPR spectra exhibiting the superhyperfine structure from benzene ring protons distant from the radical center. An analysis of the spectra shows that, regardless of the electronic effects of the substituents in the benzene ring, the superhyperfine coupling constant of an unpaired electron with the distant protons at positions 4 and 5 of the aromatic system is substantially greater than that with the protons at positions 3 and 6 that are closer to the N-oxyl radical center. This is indicative of an unusual character of the spin density distribution of the unpaired electron in substituted phthalimide-N-oxyl radicals. Understanding of the nature of the electron density distribution in imide-N-oxyl radicals may be useful for the development of commercial mediators of oxidation based on N-hydroxyimides. [ DOI ]

Пиргач Д. А., Мулина О. М., ТЕРЕНТЬЕВ А. О. Катализируемый солями меди (i) синтез β-гидроксисульфонов из стиролов и сульфонилгидразидов // Успехи в химии и химической технологии. — 2016. — Т. 30, № 11. — С. 68–69.

ПЕРСПЕКТИВЫ ПРИМЕНЕНИЯ ПРОДУЦИРУЕМЫХ ПОЧВЕННЫМИ ВОДОРОСЛЯМИ И ЦИАНОБАКТЕРИЯМИ ВЕЩЕСТВ В РАСТЕНИЕВОДСТВЕ / И. Б. КРЫЛОВ, А. С. БУДНИКОВ, Л. А. ГАЙСИНА и др. // Успехи в химии и химической технологии. — 2016. — Т. 30, № 11 (180). — С. 97–98. Создание препаратов для увеличения стрессоустойчивости сельскохозяйственных культур на основе биомассы водорослей и цианобактерий представляет экологически безопасную альтернативу использованию синтетических химических препаратов. Проблематика создания таких препаратов состоит в сложности состава биомассы и многофакторности возможного влияния условий культивации цианобактерий и водорослей на содержание активных компонентов. В работе предпринята попытка определить химические вещества, продуцируемые почвенными водорослями и цианобактериями, отвечающие за их рост-стимулирующее и антифитопатогенное действие.

Мулина О. М., Пиргач Д. А., ТЕРЕНТЬЕВ А. О. Электросинтез сульфамидов из арилсульфонилгидразидов и аминов // Успехи в химии и химической технологии. — 2016. — Т. 30, № 11. — С. 70–71.

Terent'ev A. O., Sharipov M. Y., Nikishin G. I. Cobalt-catalyzed bisperoxidation of styrenes // Russian Chemical Bulletin. — 2015. — Vol. 64, no. 5. — P. 1053–1056. A cobalt-catalyzed peroxidation of styrenes with tert-butyl hydroperoxide gives 1-aryl-1,2-bis(tert-butylperoxy)ethanes in up to 53% yields. [ DOI ]

Sabirov D. S., Terentyev A. O., Bulgakov R. G. Counting the isomers and estimation of anisotropy of polarizability of the selected c60 and c70 bisadducts promising for organic solar cells // The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment & general theory. — 2015. — Vol. 119, no. 43. — P. 10697–10705. Currently, bisadducts of C60 and C70 fullerenes are widely studied as electron-acceptor materials for organic solar cells. These compounds are usually used as mixtures of the positional isomers. However, as recently shown, the separate use of the purified isomers with lowest anisotropies of polarizability may enhance solar cell output parameters. To predict the structures of the compounds appropriate for this purpose, we calculated anisotropies of polarizability of four classes of fullerene bisadducts, namely, bis-[60]PCBM, [60]OQMF, bis-[70]PCBM, and [70]OQMF (18, 16, 41, and 42 positional isomers, respectively). As found, the anisotropies quadratically correlate with the interaddend distances in fullerene bisadducts, whereas there are no obvious correlations between the structures and lowest unoccupied molecular orbital levels, traditionally used for assessing the efficiency of candidates for organic solar cell electron acceptors. According to our calculations, bisadducts bis-[60]PCBM-ee-1, [60]OQMF-cis-3.2, [60]OQMF-trans-4.2, cc1.1cc2′.1-bis-[70]PCBM, and cc1cc2′.1-[70]OQMF have the lowest anisotropies of polarizability. These compounds have a primary interest for synthesis, purification, and further separate testing in solar cells. The structures of these adducts have a common feature, which we describe with the "not so close and not so far" rule: the distances between the addends in the most isotropic fullerene bisaddicts should be medium among the possible values. These are ee, ef, cis-3, and trans-4 positions in the case of the C60 bisadducts and cc bonds placed on the different poles and the same hemisphere of the C70 skeleton. © 2015 American Chemical Society. [ DOI ]

Krylov I. B., Vil' V. A., Terent'ev A. O. Cross-dehydrogenative coupling for the intermolecular c-o bond formation // Beilstein Journal of Organic Chemistry. — 2015. — Vol. 11. — P. 92–146. The present review summarizes primary publications on the cross-dehydrogenative C-O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C-O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C-O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C-H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C-O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C-H activation processes involving intermolecular C-O bond formation are discussed: acyloxylation reactions with ArI(O2CR)(2) reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). [ DOI ]

Elucidation of the in vitro and in vivo activities of bridged 1,2,4-trioxolanes, bridged 1,2,4,5-tetraoxanes, tricyclic monoperoxides, silyl peroxides, and hydroxylamine derivatives against schistosoma mansoni / N. Cowan, I. A. Yaremenko, I. B. Krylov et al. // Bioorganic and Medicinal Chemistry. — 2015. — Vol. 23, no. 16. — P. 5175–5181. Praziquantel is currently the only drug available to treat schistosomiasis. Since drug resistance would be a major barrier for the increasing global attempts to eliminate schistosomiasis as a public health problem, efforts should go hand in hand with the discovery of novel treatment options. Synthetic peroxides might offer a good direction since their antischistosomal activity has been demonstrated in the laboratory. We studied 19 bridged 1,2,4,5-tetraoxanes, 2 tricyclic monoperoxides, 11 bridged 1,2,4-trioxolanes, 12 silyl peroxides, and 4 hydroxylamine derivatives against newly transformed schistosomula (NTS) and adult Schistosoma mansoni in vitro. Schistosomicidal compounds were tested for cytotoxicity followed by in vivo studies of the most promising compounds. Tricyclic monoperoxides, trioxolanes, and tetraoxanes revealed the highest in vitro activity against NTS (IC(50)s 0.4-20.2 mu M) and adult schistosomes (IC(50)s 1.8-22.8 mu M). Tetraoxanes showed higher cytotoxicity than antischistosomal activity. Selected trioxolane and tricyclic monoperoxides were tested in mice harboring an adult S. mansoni infection. The highest activity was observed for two trioxolanes, which showed moderate worm burden reductions (WBR) of 44.3% and 42.9% (p > 0.05). Complexation of the compounds with beta-cyclodextrin with the aim to improve solubility and gastrointestinal absorption did not increase in vivo antischistosomal efficacy. The high in vitro antischistosomal activity of trioxolanes and tricyclic monoperoxides is a promising basis for future investigations, with the focus on improving in vivo efficacy. (C) 2015 Elsevier Ltd. All rights reserved. [ DOI ]

Lanthanide-catalyzed oxidative c-o coupling of 1,3-dicarbonyl compounds with diacyl peroxides / A. O. Terent'ev, V. A. Vil', G. I. Nikishin, W. Adam // Synlett. — 2015. — Vol. 26, no. 6. — P. 802–806. The lanthanide-catalyzed oxidative C-O coupling of -substituted 1,3-dicarbonyl compounds with diacyl peroxides (act both as oxidant and oxygen substituent) affords oxygen-functionalized adducts in up to 94% yield. The products of this convenient and efficient transformation serve as potentially valuable precursors for the synthesis of natural products and pharmaceuticals. [ DOI ]

Manganese triacetate as an efficient catalyst for bisperoxidation of styrenes / A. O. Terent'ev, M. Y. Sharipov, I. B. Krylov et al. // Organic and Biomolecular Chemistry. — 2015. — Vol. 13, no. 5. — P. 1439–1445. A method was developed for the bisperoxidation of styrenes with tert- butyl hydroperoxide in the presence of a catalytic amount of manganese(III) acetate. It was shown that compounds of manganese in oxidation states 2, 4, and 7 also catalyze this reaction. The target [1,2-bis(tert-butylperoxy)ethyl] arenes were synthesized in yields from 46 to 75%. [ DOI ]

Organocatalytic peroxidation of malonates, beta-ketoesters, and cyanoacetic esters using n-bu4ni/t-buooh-mediated intermolecular oxidative c(sp(3))-o coupling / A. O. Terent'ev, A. T. Zdvizhkov, D. O. Levitsky et al. // Tetrahedron. — 2015. — Vol. 71, no. 47. — P. 8985–8990. A new organocatalytic approach for the synthesis of peroxides based on CH activation of a sp(3)-hybridized carbon atom is reported. Peroxides were prepared in 31-89% yield by the reaction of malonates, beta-ketoesters, and cyanoacetic esters with a Bu4NI/tert-butyl hydroperoxide system. The formation of the expected hydroxylation products was not observed. In the discovered reaction, tert-butyl hydroperoxide plays a dual role by acting as the oxidant and the O-reagent for the C-O coupling. The synthesis can be scaled up to generate gram quantities of the target products. (C) 2015 Elsevier Ltd. All rights reserved. [ DOI ]

Krylov I. B., Terent'ev A. O. Oxidative c-o coupling of benzylmalononitrile with 3-(hydroxyimino)pentane-2,4-dione // Russian Journal of Organic Chemistry. — 2015. — Vol. 51, no. 1. — P. 10–13. Oxidative C-O coupling of benzylmalononitrile with 3-(hydroxyimino)pentane-2,4-dione has been accomplished. This reaction is the first example of oxidative C-O coupling of a malononitrile with an oxime. The best yield (65%) of the coupling product, 2-benzyl-2-[(2,4-dioxopent-3-ylidene)aminooxy]malononitrile, has been achieved with the use of Cu(ClO4)(2) center dot 6 H2O as oxidant. It is believed that the reaction involves intermediate formation of oxygen-centered aminoxyl radical. [ DOI ]

Primary alkanols: oxidative homocondensation in water and cross-condensation in methanol / G. I. Nikishin, L. L. Sokova, A. O. Terent'ev, N. I. Kapustina // Russian Chemical Bulletin. — 2015. — Vol. 64, no. 12. — P. 2845–2850. Water was used as a reaction medium and a reagent in oxidation of primary alkanols to dimeric esters and alkanoic acids using either molecular bromine or a hydrogen peroxide-hydrobromic acid mixture as the oxidants. The similar reaction in methanol produced methyl alkanoates. [ DOI ]

Stereoelectronic source of the anomalous stability of bis-peroxides / d. P. Gomes Gabriel, V. A. Vil', A. O. Terent'ev, I. V. Alabugin // Chemical science. — 2015. — Vol. 6, no. 12. — P. 6783–6791. The unusual stability of bis- and tris-peroxides contradicts the conventional wisdom-some of them can melt without decomposition at temperatures exceeding 100 degrees C. In this work, we disclose a stabilizing stereoelectronic effect that two peroxide groups can exert on each other. This stabilization originates from strong anomeric n(O) -> sigma(CO)* interactions that are absent in mono-peroxides but reintroduced in molecules where two peroxide moieties are separated by a CH2 group. Furthermore, such effects can be induced by other s-acceptors and amplified by structural constraints imposed by cyclic and bicyclic frameworks. [ DOI ]

Synthesis of peroxides from beta,delta-triketones under heterogeneous conditions / A. O. Terent'ev, I. A. Yaremenko, A. P. Glinushkin, G. I. Nikishin // Russian Journal of Organic Chemistry. — 2015. — Vol. 51, no. 12. — P. 1681–1687. Heterogeneous reactions of beta,delta-triketones with ethereal hydrogen peroxide in nonpolar solvents, catalyzed by phosphomolybdic acid, afforded mixtures of stereoisomeric ozonides, tricyclic monoperoxides, and bridged tetraoxanes. The trioxolane ring is formed by the carbonyl groups located in the delta-position with respect to each other. [ DOI ]

Терентьев А. О., Шарипов М. Ю., Никишин Г. И. КАТАЛИЗИРУЕМОЕ СОЛЯМИ КОБАЛЬТА БИСПЕРОКСИДИРОВАНИЕ СТИРОЛОВ // Известия Академии наук. Серия химическая. — 2015. — С. 1053–1056.

A convenient synthesis of cyclopropane malonyl peroxide / A. O. Terent'ev, V. A. Vil, O. M. Mulina et al. // Mendeleev Communications. — 2014. — Vol. 24, no. 6. — P. 345–345. Cyclopropane-1,1-dicarbonyl peroxide was prepared in 85% yield by the reaction of diethyl cyclopropane-1,1-dicarboxylate with the urea hydrogen peroxide clathrate in the presence of methanesulfonic acid. [ DOI ]

A convenient synthesis of сyclopropane malonyl peroxide / A. O. Terent’ev, V. A. Vil’, O. M. Mulina и др. // Mendeleev Communications. — 2014. — Т. 24. — С. 345. [ DOI ]

Approach for the preparation of various classes of peroxides based on the reaction of triketones with h2o2: First examples of ozonide rearrangements / I. A. Yaremenko, A. O. Terent'ev, V. A. Vil' et al. // Chemistry - A European Journal. — 2014. — Vol. 20, no. 32. — P. 10160–10169. [ DOI ]

Cyclobutyl- and cyclobutenylphosphonates: Synthesis, transformations and biological activities / A. A. Aziz Al Quntar, S. Morris, A. O. Terent’ev, V. M. Dembitsky // Mini-Reviews in Organic Chemistry. — 2014. — Vol. 11. — P. 445–461. [ DOI ]

Iminoxyl radical-based strategy for intermolecular c-o bond formation: Cross-dehydrogenative coupling of 1,3-dicarbonyl compounds with oximes / I. B. Krylov, A. O. Terent'ev, V. P. Timofeev et al. // Advanced Synthesis and Catalysis. — 2014. — Vol. 356, no. 10. — P. 2266–2280. Cross-dehydrogenative C-O coupling of 1,3-diketones and 1,3-keto esters with oximes was realized for the first time. The reaction proceeds in the presence of the oxidants [KMnO4, Mn(OAc)(2)/KMnO4, Mn(OAc)(3)center dot 2H(2)O, MnO2, Mn(acac)(3), Fe(ClO4)(3), Cu(ClO4)(2)center dot 6H(2)O, Cu(NO3)(2)center dot 2.5H(2)O, and (NH4)(2)Ce(NO3)(6)]. Twenty cross-coupling products were synthesized using potassium permanganate (KMnO4), manganese(II) acetate dihydrate [Mn(OAc)(3)center dot 2H(2)O], or the manganese(II) acetate/potassium permanganate [Mn(OAc)(2)/KMnO4] system; yields are 27-92%. The synthesis can be easily scaled up to gram quantities of the target products. Apparently, the reaction proceeds via a radical mechanism in which the oxidizing agent serves to generate radicals from oximes and perform the one-electron oxidation of 1,3-dicarbonyl compounds. The formation of oxime radicals was confirmed quantitatively by electron spin resonance (ESR) spectroscopy. The coupling described in the present study is the first example of the selective intermolecular reaction involving unstable iminoxyl radicals generated in situ. [ DOI ]

Inverted thermochemistry of "norbornadiene-quadricyclane" molecular system inside fullerene nanocages / D. S. Sabirov, A. O. Terentyev, I. S. Shepelevich, R. G. Bulgakov // Computational and Theoretical Chemistry. — 2014. — Vol. 1045. — P. 86–92. Currently, endofullerenes become common compounds that enrich chemistry by novel opportunities for molecular engineering. The influence of the fullerene cages on the behavior of guest molecules is obvious and not limited to simple encaging. Unfortunately, its quantitative estimation is difficult but this information may provide insights into regulating reactions by encapsulation. In the present work, we have applied the accurate DFT techniques to elucidate how encapsulation into the fullerene cages changes thermodynamic parameters and polarizability of "norbornadiene. ↔. quadricyclane" interconversion (a classic example of molecular systems for solar energy accumulation). As it is turned out, decreasing the size of the cage enhances thermodynamic favorability of the norbornadiene conversion. Moreover, when appropriately encapsulating, the primarily endothermic direct reaction becomes exothermic. This also holds true in the case of inorganic (boron-nitrogen) fullerenes with rigid structures. Thus, the found regularity is a general trend and encapsulation can be recommended as one of the ways to tune thermodynamic parameters of chemical reactions. © 2014 Elsevier B.V. [ DOI ]

Nature chooses rings: Synthesis of silicon-containing macrocyclic peroxides / A. V. Arzumanyan, R. A. Novikov, A. O. Terent'ev et al. // Organometallics. — 2014. — Vol. 33, no. 9. — P. 2230–2246. [ DOI ]

Terent’ev A. O., Krylov I. B., Lipatnikov A. D. Oxidative coupling of n-hydroxyphthalimide with toluene // Russian Journal of General Chemistry. — 2014. — Vol. 84, no. 11. — P. 2084–2087. [ DOI ]

Peroxidation of beta-diketones and beta-keto esters with tert-butyl hydroperoxide in the presence of cu(clo4)(2)/sio2 / A. Terent'ev, V. Vil, O. Bityukov, G. Nikishin // Russian Chemical Bulletin. — 2014. — Vol. 63, no. 11. — P. 2461–2466.

Sabirov D. S., Terentyev A. O., Bulgakov R. G. Polarizability of fullerene [2+2]-dimers: A dft study // Physical Chemistry Chemical Physics. — 2014. — Vol. 16, no. 28. — P. 14594–14600. Currently, the exaltation of polarizability of (C60)2 dimers has been predicted with DFT-methods (D. Sh. Sabirov, RSC Adv., 2013, 3(42), 19430). It consists of an increase in the polarizability when two C 60 molecules are united, forming a [2+2]-dimer. In the present work, we point attention to the bicage structures of the other fullerenes, which are promising compounds for nano-applications. We have performed the first density-functional theory study on the polarizability of fullerene [2+2]-dimers (Cn)2 (n = 20, 24, 30, 36, 50, and 70) and shown that the exaltation of polarizability is typical for all the members of the fullerenes family. © the Partner Organisations 2014. [ DOI ]

Preparation of a microsized cerium chloride-based catalyst and its application in the michael addition of beta-diketones to vinyl ketones / A. O. Terent'ev, V. A. Vil', I. A. Yaremenko et al. // New Journal of Chemistry. — 2014. — Vol. 38, no. 4. — P. 1493–1502. [ DOI ]

Reactions of mono- and bicyclic enol ethers with the i2–hydroperoxide system / A. O. Terent'ev, A. T. Zdvizhkov, A. N. Kulakova et al. // RSC advances. — 2014. — Vol. 4. — P. 7579–7587.

Reactions of mono- and bicyclic enol ethers with the i2–hydroperoxide system / A. O. Terent'ev, A. T. Zdvizhkov, A. N. Kulakova et al. // RSC advances. — 2014. — Vol. 4. — P. 7579–7587. [ DOI ]

Six peroxide groups in one molecule - synthesis of nine-membered bicyclic silyl peroxides / A. V. Arzumanyan, A. O. Terent'ev, R. A. Novikov et al. // European Journal of Organic Chemistry. — 2014. — no. 31. — P. 6877–6883. [ DOI ]

Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products / A. O. Terent'ev, D. A. Borisov, V. A. Vil’, V. M. Dembitsky // Beilstein Journal of Organic Chemistry. — 2014. — Vol. 10. — P. 34–114. [ DOI ]

Терентьев А. О., Крылов И. Б., Липатников А. Д. ОКИСЛИТЕЛЬНОЕ СОЧЕТАНИЕ n-ГИДРОКСИФТАЛИМИДА С ТОЛУОЛОМ // Журнал общей химии. — 2014. — Т. 84, № 11. — С. 1786–1789.

Пероксидирование β-дикетонов и β-кетоэфиров трет-бутилгидропероксидом в присутствии cu(clo4)2/sio2 / А. О. Терентьев, В. А. Виль, О. В. Битюков, Г. И. Никишин // Известия Академии наук. Серия химическая. — 2014. — № 11. — С. 2461–2466.

Развитие методологии современного селективного органического синтеза: получение функционализированных молекул с атомарной точностью / В. П. Анаников, Л. Л. Хемчян, Ю. В. Иванова и др. // Russian Chemical Reviews. — 2014. — Т. 83, № 10. — С. 885–985. [ DOI ]

Развитие методологии современного селективного органического синтеза: получение функционализированных молекул с атомарной точностью / В. П. Анаников, Л. Л. Хемчян, Ю. В. Иванова и др. // Успехи химии. — 2014. — Т. 83, № 10. — С. 885–985. [ DOI ]

Dembitsky V. M., Terent’ev A. O., Levitsky D. O. Aziridine alkaloids: Origin, chemistry and activity // NATURAL PRODUCTS JOURNAL. — 2013. — P. 977–1006.

Boron trifluoride as an efficient catalyst for the selective synthesis of tricyclic monoperoxides from beta,delta-triketones and h2o2 / A. O. Terent'ev, I. A. Yaremenko, V. A. Vil' et al. // SYNTHESIS-STUTTGART. — 2013. — Vol. 45, no. 2. — P. 246–250. Boron trifluoride was found to serve as an efficient catalyst for the reaction of beta,delta-triketones with H2O2 producing tricyclic monoperoxides in yields from 48-93%. BF3 acts simultaneously as a catalyst and co-solvent. The synthesis can be scaled up to tens of grams. The resulting peroxides can be easily isolated from the reaction mixture by column chromatography. [ DOI ]

Cyclic peroxides and related initiating systems for radical polymerization of methyl methacrylate / R. M. Islamova, O. I. Ishkinina, S. V. Nazarova et al. // Russian Chemical Bulletin. — 2013. — Vol. 62. — P. 1282–1285.

Oxidative c-o cross-coupling of 1,3-dicarbonyl compounds and their heteroanalogues with n-substituted hydroxamic acids and n-hydroxyimides / A. O. Terent’ev, I. B. Krylov, V. P. Timofeev et al. // Advanced Synthesis and Catalysis. — 2013. — Vol. 355. — P. 2375–2390. [ DOI ]

Phosphomolybdic and phosphotungstic acids as efficient catalysts for the synthesis of bridged 1,2,4,5-tetraoxanes from beta-diketones and hydrogen peroxide / A. O. Terent'ev, I. A. Yaremenko, V. A. Vil' et al. // Organic and Biomolecular Chemistry. — 2013. — Vol. 11, no. 16. — P. 2613–2623.

Synthesis and antifungal activity of arylthiocyanates / V. A. Kokorekin, A. O. Terent'ev, G. V. Ramenskaya et al. // Pharmaceutical Chemistry Journal. — 2013. — Vol. 47, no. 8. — P. 422–425. [ DOI ]

КИНЕТИКА ЭЛЕКТРОХИМИЧЕСКОГО ОКИСЛЕНИЯ 1,1-бис-ГИДРОПЕРОКСИ-4-МЕТИЛЦИКЛОГЕКСАНА НА ПЛАТИНЕ / М. Д. Веденяпина, А. П. Симакова, М. М. Платонов и др. // Журнал физической химии. — 2013. — Т. 87, № 3. — С. 418–421.

Синтез и противогрибковая активность арилтиоцианатов / В. А. Кокорекин, А. О. Терентьев, Г. В. Раменская и др. // Химико-фармацевтический журнал. — 2013. — Т. 47, № 8. — С. 26–29.

Chemiluminescence from the biomimetic reaction of 1,2,4-trioxolanes and 1,2,4,5-tetroxanes with ferrous ions / D. V. Kazakov, A. R. Timerbaev, F. E. Safarov et al. // RSC advances. — 2012. — Vol. 2, no. 1. — P. 107–110. The 1,2,4-trioxolane and 1,2,4,5-tetroxane pharmacophores are currently considered as the next generation of synthetic antimalarial drugs. This fact has stimulated the exploration of the chemiluminescence displayed by these cyclic peroxides in biomimetic reactions with Fe(II). The CL has been induced by FeSO(4) and/or the FeCl(3)/L-cysteine/Rhodamine G system in aqueous (50%) acetonitrile. The light emission in the visible spectral region has been recorded for triterpenoid-based 1,2, 4-trioxolanes, purely synthetic ozonide OZ03, bicyclic 1,2,4, 5-tetroxanes, a tetroxane derived from deoxycholic acid, the diperoxide of trifluoroacetone, as well as the natural artemisinin. The herein discovered CL provides a promising perspective for the study of pharmacologically active peroxides in biomedical applications. [ DOI ]

Chemiluminescence of 1,2,4-trioxolanes and 1,2,4,5-tetroxanes: fundamentals and possible biomedical applications / D. V. Kazakov, F. E. Safarov, T. A. Nazirov et al. // Luminescence : the journal of biological and chemical luminescence. — 2012. — Vol. 27, no. 2. — P. 125–125.

Terent'ev A. O., Borisov D. A., Yaremenko I. A. General methods for the preparation of 1,2,4,5-tetraoxanes - key structures for the development of peroxidic antimalarial agents // Chemistry of Heterocyclic Compounds. — 2012. — Vol. 48, no. 1. — P. 55–58. General methods are presented for the preparation of symmetric and asymmetric 1,2,4,5-tetraoxanes, based on peroxidation of carbonyl compounds and their derivatives. [ DOI ]

Generation and cross-coupling of benzyl and phthalimide-n-oxyl radicals in a cerium(iv) ammonium nitrate/n-hydroxyphthalimide/arch2r system / A. O. Terent'ev, I. B. Krylov, M. Y. Sharipov et al. // Tetrahedron. — 2012. — Vol. 68, no. 50. — P. 10263–10271. A method was developed for the cross-dehydrogenative coupling of alkylarenes and related compounds with N-hydroxyphthalimide (NHPI) using cerium(IV) ammonium nitrate (CAN) to prepare O-substituted NHPI derivatives. The characteristic feature of the reaction is that NHPI plays a dual role. Thus, in the presence of CAN, NHPI generates the phthalimide-N-oxyl (PINO) radical, which abstracts a hydrogen atom from the benzyl position to form a C-centered radical. The target oxidative cross-coupling product is formed mainly through the recombination of PINO with the C-centered radical. Therefore, NHPI serves as a mediator for the radical process and a reagent for the radical cross-coupling. The target products were obtained in yields from 35 to 80%. (c) 2012 Elsevier Ltd. All rights reserved. [ DOI ]

Identification of antischistosomal leads by evaluating bridged 1,2,4,5-tetraoxanes, alphaperoxides, and tricyclic monoperoxides / K. Ingram, I. A. Yaremenko, I. B. Krylov et al. // Journal of Medicinal Chemistry. — 2012. — Vol. 55, no. 20. — P. 8700–8711. Although antischistosomal properties of peroxides were studied in recent years, systematic structure activity relationships have not been conducted. We evaluated the antischistosomal potential of 64 peroxides belonging to bridged 1,2,4,5-tetraoxanes, alphaperoxides, and tricyclic monoperoxides. Thirty-nine compounds presented IC50 values <15 mu M on newly transformed schistosomula. Active drugs featured phenyl-, adamantane-, or alkyl residues at the methylene bridge. Lower susceptibility was documented on adult schistosomes, with most hit compounds being tricyclic monoperoxides (IC50: 7.7-13.4 mu M). A bridged 1,2,4,5-tetraoxane characterized by an adamantane residue showed the highest activity (IC50: 0.3 mu M) on adult Schistosoma mansoni. Studies with hemin and heme supplemented medium indicated that antischistosomal activation of peroxides is not necessarily triggered by iron porphyrins. Two compounds (tricyclic monoperoxide; bridged 1,2,4,5-tetraoxane) revealed high worm burden reductions in the chronic (WBR: 75.4-82.8%) but only moderate activity in the juvenile (WBR: 18.9-43.1%) S. mansoni mouse model. Our results might serve as suiting point for the preparation and evaluation of related derivatives. [ DOI ]

Selective synthesis of cyclic peroxides from triketones and h2o2 / A. O. Terent'ev, I. A. Yaremenko, V. V. Chernyshev et al. // Journal of Organic Chemistry. — 2012. — Vol. 77, no. 4. — P. 1833–1842. A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and acetal moieties was developed based on the acid-catalyzed reaction of beta,delta-triketones with H2O2. Tricyclic compounds are formed selectively in yields from 39% to 90% by the reactions with the use of large amounts of strong acids, such as H2SO4, HClO4, or HBF4, which act both as the catalyst and as the co-solvent. The reaction is unusual in that, despite the diversity of possible peroxidation pathways giving cyclic compounds and oligomers, the reaction proceeds with high selectivity and produces tricyclic peroxides via the monoperoxidation of the carbonyl groups in the beta-positions and the transformation of the delta-carbonyl group into the acetal one. The syntheses are scaled up to tens of grams, and the resulting peroxides can be easily isolated from the reaction mixture. [ DOI ]

Synthesis of dibromo ketones by the reaction of the environmentally benign h2o2-hbr system with oximes / A. O. Terent'ev, I. B. Krylov, V. A. Vil' et al. // Central European Journal of Chemistry. — 2012. — Vol. 10, no. 2. — P. 360–367. It was found that oximes undergo deoximation in the presence of the H2O2aq-HBraq system to form ketones and bromo ketones. This reaction provided the basis for the synthesis of dibromo ketones in yields varying from 40% to 94%. This method is environmentally friendly, sustainable, and easy to perform. The results of this investigation extend the potential of the use of oximes for the protection of carbonyl group, thus offering the ability to perform not only conventional deoximation but also the subsequent bromination of ketones. The reaction is easily scaled up and dibromo ketones can be prepared in gram amounts. [ DOI ]

Терентьев А. О., Борисов Д. А., Яременко И. А. ОСНОВНЫЕ МЕТОДЫ ПОЛУЧЕНИЯ 1,2,4,5-ТЕТРАОКСАНОВ – КЛЮЧЕВЫХ СТРУКТУР ДЛЯ РАЗРАБОТКИ ПЕРОКСИДНЫХ АНТИМАЛЯРИЙНЫХ СРЕДСТВ // ХГС. — 2012. — Т. 1. — С. 60–63.

ЭЛЕКТРОХИМИЧЕСКОЕ ПОВЕДЕНИЕ МОСТИКОВОГО 1,2,4,5-ТЕТРАОКСАНА / М. Д. Веденяпина, А. П. Симакова, Д. А. Борисов и др. // Конденсированные среды и межфазные границы. — 2012. — Т. 14, № 3. — С. 297–305.

Chemiluminescence as a base for a new approach to the study of pharmacologically promising peroxide agents / D. V. Kazakov, O. B. Kazakova, G. Y. Ishmuratov et al. // Doklady Chemistry. — 2011. — Vol. 436. — P. 34–38. [ DOI ]

Electrochemical oxidation of 1,1-dihydroxy-4-methylcyclohexane on platinum anode. synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane / M. D. Vedenyapina, A. O. Terent'ev, M. M. Platonov et al. // Russian Journal of Electrochemistry. — 2011. — Vol. 47, no. 2. — P. 234–237. The possibility is shown of electrochemical synthesis of 3,12-dimethyl-7,8,15,16-tetraoxadispiro[5.2.5.2]hexadecane that belong to the class of 1,2,4,5-tetraoxanes by oxidation of 1,1-dihydroperoxy-4-methylcyclohexane using a Pt anode. [ DOI ]

Organic silicon and germanium peroxides: synthesis and reactions / A. O. Terent'ev, M. M. Platonov, D. O. Levitsky, V. M. Dembitsky // Russian Chemical Reviews. — 2011. — Vol. 80, no. 9. — P. 807–828. [ DOI ]

Selective synthesis of unsymmetrical peroxides: Transition-metal-catalyzed oxidation of malononitrile and cyanoacetic ester derivatives by tert-butyl hydroperoxide at the alpha-position / A. O. Terent'ev, D. A. Borisov, V. V. Semenov et al. // SYNTHESIS-STUTTGART. — 2011. — no. 13. — P. 2091–2100. A novel method was developed for the selective oxidation of alpha-monosubstituted malononitrile and cyanoacetic ester derivatives at the alpha-position based on transition-metal-catalyzed reaction (Cu, Fe, Mn, Co) with tert-butyl hydroperoxide giving unsymmetrical peroxides in 63-94% yields. The method is facile, does not require large excesses of reagents, and is amenable to gram-scale synthesis. [ DOI ]

Органические пероксиды кремния и германия: синтез и реакции / А. О. Терентьев, М. М. Платонов, Д. О. Левицкий, В. М. Дембицкий // Успехи химии. — 2011. — Т. 80, № 9. — С. 843–864.

Хемилюминесценция – основа нового подхода к исследованию фармакологически перспективных агентов пероксидной природы / Д. В. Казаков, О. Б. Казакова, Г. Ю. Ишмуратов и др. // Доклады Академии наук. — 2011. — Т. 436, № 6. — С. 774–779.

Электрохимическое окисление 1,1-дигидроперокси-4-метилциклогексана на платиновом аноде. Синтез 3,12-диметил-7,8,15,16-тетраоксадиспиро[5.2.5.2]гексадекана / М. Д. Веденяпина, А. О. Терентьев, М. М. Платонов и др. // Электрохимия. — 2011. — Т. 47, № 2. — С. 251–254.

A new property of geminal bishydroperoxides: hydrolisis with the removal of hydroperoxide groups to form of a ketone / A. O. Terent'ev, O. B. Krivykh, I. B. Krylov et al. // Russian Journal of General Chemistry. — 2010. — Vol. 80, no. 8. — P. 1667–1671. [ DOI ]

Dembitsky V. M., Terent'ev A. O., Levitsky D. O. Amino and fatty acids of wild edible mushrooms of the genus boletus // Records of Natural Products. — 2010. — P. 218–223.

AНТИМИКРОБНАЯ АКТИВНОСТЬ ГЕМИНАЛЬНЫХ БИСГИДРОПЕРОКСИДОВ / В. И. Тропина, О. В. Кривых, Н. П. Садчикова и др. // Химико-фармацевтический журнал. — 2010. — Т. 44. — С. 16–18.

Nanocomposites based on polymethylmethacrylate and silica / D. A. Sapozhnikov, a. Email, A. A. Sakharova et al. // Bulletin of the Russian Academy of Sciences: Physics. — 2010. — Vol. 74. — P. 1039–1042.

Oxidation of substituted beta-diketones with hydrogen peroxide: Synthesis of esters through the formation of bridged 1,2,4,5-tetraoxanes / A. O. Terent'ev, D. A. Borisov, I. A. Yaremenko et al. // SYNTHESIS-STUTTGART. — 2010. — no. 7. — P. 1145–1149. Acid-catalyzed oxidation of alkyl- and benzyl-substituted beta-diketones by hydrogen peroxide at 79-120 degrees C in a mixture of an alcohol and a strong acid (sulfuric acid, tetrafluoroboric acid, or perchloric acid) gave the corresponding esters through the formation of bridged 1,2,4,5-tetraoxanes. [ DOI ]

Synthesis and antimicrobial activity of geminal bis-hydroperoxides / V. I. Tropina, O. V. Krivykh, N. P. Sadchikova et al. // Pharmaceutical Chemistry Journal. — 2010. — Vol. 44, no. 5. — P. 248–250. [ DOI ]

Synthesis of asymmetric peroxides: Transition metal (cu, fe, mn, co)-catalyzed peroxidation of beta-dicarbonyl compounds with tert-butyl hydroperoxide / A. Terent'ev, D. Borisov, I. Yaremenko et al. // Journal of Organic Chemistry. — 2010. — Vol. 75. — P. 5065–5071.

Нанокомпозиты на основе полиметилметакрилата и силикагеля / Д. А. Сапожников, А. А. Сахарова, Т. В. Волкова и др. // Известия Академии наук СССР, серия физическая. — 2010. — Т. 74. — С. 1081–1084.

Новое свойство геминальных бисгидропероксидов ­­– гидролиз с отщеплением гидропероксидных групп и образованием кетонов / А. О. Терентьев, О. В. Кривых, И. Б. Крылов и др. // Журнал общей химии. — 2010. — Т. 80, № 8. — С. 1355–1359.

Terent'Ev A. V., Varfolomeeva V. V., Buryak A. K. Calculation of henry constants for the adsorption of isomeric phenylenediamines on graphitized thermal carbon black // Russian Journal of Physical Chemistry A. — 2009. — Vol. 83. — P. 2331–2335.

Facile and selective procedure for the synthesis of bridged 1,2,4,5-tetraoxanes; strong acids as cosolvents and catalysts for addition of hydrogen peroxide to beta-diketones / A. O. Terent’ev, D. A. Borisov, V. V. Chernyshev, G. I. Nikishin // Journal of Organic Chemistry. — 2009. — Vol. 74. — P. 3335–3340.

First synthesis of cyclic organogermanium peroxides, 1,2,4,5,7,8-hexaoxa-3-germonanes / A. O. Terent’ev, M. M. Platonov, I. V. Krylova et al. // Journal of Organometallic Chemistry. — 2009. — P. 1786–1788.

Reaction of enol ethers with the i2–h2o2 system: Synthesis of 2-iodo-1-methoxyhydroperoxides and their deperoxidation and demethoxylation to 2-iodoketones / A. O. Terent’ev, A. M. Borisov, M. M. Platonov et al. // SYNTHESIS-STUTTGART. — 2009. — P. 4159–4166.

Ring contraction of 1,2,4,5,7,8-hexaoxa-3-silonanes by selective reduction of coosi fragments. synthesis of new silicon-containing rings, 1,3,5,6-tetraoxa-2-silepanes / A. O. Terent’ev, M. M. Platonov, A. I. Tursina et al. // Journal of Organic Chemistry. — 2009. — Vol. 74. — P. 1917–1922.

Варфоломеева В. В., Терентьев А. В., Буряк А. К. ВЛИЯНИЕ ВНУТРИМОЛЕКУЛЯРНОЙ ВОДОРОДНОЙ СВЯЗИ НА ХРОМАТОГРАФИЧЕСКОЕ ПОВЕДЕНИЕ ФЕНИЛАЛКИЛАМИНОВ // Журнал физической химии. — 2009. — Т. 83. — С. 655–660.

Синтез 1,2,4,5,7,8-гексаоксонанов катализируемой иодом реакцией 1,1’-дигидропероксиди(циклоалкил)пероксидов с кеталями / А. О. Терентьев, М. М. Платонов, И. Б. Крылов, Г. И. Никишин // Известия Академии наук Молдовы. Серия химическая. — 2009. — Т. 2. — С. 333–336.

Варфоломеева В. В., Терентьев А. В., Буряк А. К. ВЛИЯНИЕ ВНУТРИМОЛЕКУЛЯРНОЙ ВОДОРОДНОЙ СВЯЗИ НА АДСОРБЦИОННЫЕ СВОЙСТВА АРОМАТИЧЕСКИХ СПИРТОВ И ТИОЛОВ // Журнал физической химии. — 2008. — Т. 82. — С. 1033–1038.

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