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.
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 ]
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 ]
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.
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 ]
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 ]
Synthetic strategies for peroxide ring construction in artemisinin / V. Vil’, I. Yaremenko, A. Ilovaisky, A. Terent’ev // Molecules. — 2017. — Vol. 22, no. 1. — P. 117.
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 ]
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 ]
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 ]
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 ]
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 ]
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 ]
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 ]
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 ]
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.
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 ]
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. — P. 1833–1842. [ 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.
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 of asymmetric peroxides: Transition metal (cu, fe, mn, co) catalyzed peroxidation of beta-dicarbonyl compounds with tert-butyl hydroperoxide / A. O. Terent'ev, D. A. Borisov, I. A. Yaremenko et al. // Journal of Organic Chemistry. — 2010. — Vol. 75, no. 15. — P. 5065–5071. The transition metal (Cu, Fe, Mn, Co) catalyzed peroxidation of beta-dicarbonyl compounds at the a. position by tert-butyl hydroperoxide was discovered. A selective, experimentally convenient, and gram-scale method was developed for the synthesis of alpha-peroxidated derivatives of beta-diketones, beta-keto esters, and diethyl malonate. Virtually stoichiometric (2-3/1) molar ratios of tert-butyl hydroperoxide and a dicarbonyl compound were used in the reactions with beta-diketones and beta-keto esters. The target compounds were synthesized in the highest yields from beta-keto esters (45-90%) and in somewhat lower yields from beta-diketones (46-75%) and malonates (37-67%). [ 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.