Papers by Alexander Terent'ev
Advanced Synthesis & Catalysis
Advanced Synthesis & Catalysis, 2022
The newly emerged severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) cause life-threate... more The newly emerged severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) cause life-threatening diseases in millions of people worldwide and there is an urgent need for antiviral agents against this infection. While in vitro activities of artemisinins (containing endoperoxide moiety) and chloroquine (containing quinoline subunit) against SARS-CoV-2 have recently been demonstrated, no study of artemisinin- and quinoline-based hybrids has been reported yet. However, the hybrid drug’s properties can be improved compared to its parent compounds and effective new agents can be obtained by modification/hybridization of existing drugs. In this study, fifteen artemisinin- and quinoline-containing hybrid compounds were synthesized and analyzed in vitro for the first time for their inhibitory activity against SARS-CoV-2 in a cytopathic effect reduction assay. All artesunic acid-containing hybrids display superior potency against SARS-CoV-2 (EC50 values 7.8 – 46 μM) and show low or no cy...
Advanced Synthesis & Catalysis, 2020
Advanced Synthesis & Catalysis, 2020
Chemistry – A European Journal, 2020
Catalyst development for the synthesis of ozonides and tetraoxanes under heterogeneous conditions... more Catalyst development for the synthesis of ozonides and tetraoxanes under heterogeneous conditions. Disclosure of an unprecedented class of fungicides for agricultural application
ChemMedChem, 2020
This article discloses a new horizon for the application of peroxides in medical chemistry. Stabl... more This article discloses a new horizon for the application of peroxides in medical chemistry. Stable cyclic peroxides demonstrated cytotoxic activity against cancer cells, besides a mechanism of cytotoxic action was proposed. Synthetic bridged 1,2,4,5-tetraoxanes and ozonides were effective against HepG2 cancer cells and some ozonides selectively targeted on liver cancer cells (SI for compounds 11b and 12a is 8 and 5 respectively). Tetraoxanes and ozonides in some cases were more selective than paclitaxel, artemisinin, and artesunic acid. Annexin V flow cytometry analysis revealed that the active ozonides 22a and 23a induced cell death of HepG2 via apoptosis. Further study showed that compounds 22a and 23a exhibited the strong inhibitory effect on Pglycoprotein (P-gp/ABCB5) overexpressing HepG2 cancer cells. ABCB5 is a key player in the multidrug-resistant phenotype on liver cancer. Peroxides failed to demonstrate a direct correlation between oxidative potential and their biological activity. To our knowledge for the first time it was found, that peroxide diastereoisomers seemed to show stereospecific antimalarial action against the chloroquine sensitive 3D7 strain of P. falciparum. Stereoisomeric ozonide 12b is 11-times more active than stereoisomeric ozonide 12a (IC50 5.81 µM vs IC50 65.18 µM). Current findings merit further investigation of ozonides as potential therapeutic agents for drug-resistant hepatocellular carcinoma.
European Journal of Organic Chemistry, 2019
Regioselective Baeyer-Villiger oxidation of estrone and androstane derivatives into 17a-oxa-D-hom... more Regioselective Baeyer-Villiger oxidation of estrone and androstane derivatives into 17a-oxa-D-homosteroids using BF3⸱Et2O and H2O2 was developed. An important feature of this reaction lies in the selective formation of oxidation products in moderate to high yields using BF3⸱Et2O / H2O2 system traditionally applied for peroxide synthesis.
Applied microbiology and biotechnology, Jan 10, 2018
Peroxides represent a large and interesting group of biologically active natural compounds. All t... more Peroxides represent a large and interesting group of biologically active natural compounds. All these metabolites contain a peroxide group (R-O-O-R). This review describes studies of more than 60 peroxides isolated from plants and fungi. Most of the plant peroxy steroids exhibit high antiprotozoal (Plasmodium) activity with a confidence of up to 95%, while steroids harvested from fungi show more antineoplastic activity with a confidence of up to 94%. In addition, more than 20 different activities of both groups of peroxides with a probability of 78 to 90% have also been predicted using computer program PASS.
ChemMedChem, Jan 22, 2018
Twenty six peroxides belonging to bridged 1,2,4,5-tetraoxanes, bridged 1,2,4-trioxolanes (ozonide... more Twenty six peroxides belonging to bridged 1,2,4,5-tetraoxanes, bridged 1,2,4-trioxolanes (ozonides), and tricyclic monoperoxides were evaluated for the 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 highest cytotoxicity on HepG2 (IC50 0.19-0.59 µM) and some of these compounds selectively targeted liver cancer (SI for compounds 13a and 14a is 20 and 28 respectively), which in some cases were higher than that of paclitaxel, artemisinin, artesunic acid. In contrast same ozonides have shown only moderate antimalarial activity against the chloroquine sensitive 3D7 strain of P. falciparum (IC50 from 2.76 to 24.2 µM; 12b IC50 2.76 µM, 13a IC50 20.14 µM, 14a IC50 6.32 µM). These results suggest divergent mechanism of action of these deriv...
Molecules (Basel, Switzerland), Jan 11, 2017
The present review summarizes publications on the artemisinin peroxide fragment synthesis from 19... more The present review summarizes publications on the artemisinin peroxide fragment synthesis from 1983 to 2016. The data are classified according to the structures of a precursor used in the key peroxidation step of artemisinin peroxide cycle synthesis. The first part of the review comprises the construction of artemisinin peroxide fragment in total syntheses, in which peroxide artemisinin ring resulted from reactions of unsaturated keto derivatives with singlet oxygen or ozone. In the second part, the methods of artemisinin synthesis based on transformations of dihydroartemisinic acid are highlighted.
ChemInform, 2010
ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Beilstein Journal of Organic Chemistry, 2016
This review is the first to collate and summarize main data on named and unnamed rearrangement re... more 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, Kornblum−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.
The Journal of organic chemistry, Jan 8, 2016
The lanthanide-catalyzed oxidative С-O coupling of 1,3-dicarbonyl compounds with diacyl peroxides... more The lanthanide-catalyzed oxidative С-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 С-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 proc...
The Journal of Physical Chemistry A, 2016
Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl rad... more 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-Noxyl 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.
Chemical Science, 2015
The unusual stability of molecules with multiple peroxide units has stereoelectronic origin and s... more The unusual stability of molecules with multiple peroxide units has stereoelectronic origin and stems from reactivation of anomeric interactions.
FIELD: chemistry. ^ SUBSTANCE: present invention relates to a method of producing ketopantolacton... more FIELD: chemistry. ^ SUBSTANCE: present invention relates to a method of producing ketopantolactone, which is widely used in synthesis of pantothenic acid (vitamin B5), as well as other biologically active substances. The method of producing ketopantolactone involves oxidative dehydrogenation of pantolactone under the action of electrochemically generated bromine from a bromide anion source in an electrolysis cell equipped with an anode, a cathode and a stir-bar in the medium of a chlorine-containing organic solvent in a two-phase system containing an organic and an aqueous layer while passing electrical current of 4-6 F per 1 mole pantolactone and stirring the reaction mass at a rate of 1-4 rps at temperature 35-70C and pH of the medium equal to 0.5-1.5. ^ EFFECT: simple technology of producing ketopantolactone, avoiding the need to use dangerous (poisonous) and hard to handle molecular bromine, high conversion of the starting pantolactone and high output of the end product which re...
ChemInform, 2010
ABSTRACT 5,(n + 6)-Dimethoxy-1-oxabicyclo[n .4.0]alkanes undergo a previously unknown oxidative r... more ABSTRACT 5,(n + 6)-Dimethoxy-1-oxabicyclo[n .4.0]alkanes undergo a previously unknown oxidative rearrangement into ω-(2-methoxytetra-hydrofur-2-yl)alkanoic esters during electrolysis in methanol.
Natural Products, 2013
This chapter describes research on natural aziridine alkaloids isolated from both terrestrial and... more This chapter describes research on natural aziridine alkaloids isolated from both terrestrial and marine species, as well as their lipophilic semisynthetic and/or synthetic analogues. Over 100 biologically active aziridine-containing compounds demonstrate confirmed pharmacological activity including antitumor, antimicrobial, and antibacterial effects. The structures, origin, and biological activities of aziridine alkaloids are reviewed. Consequently, this
Bioorganic & medicinal chemistry, Jan 14, 2015
Praziquantel is currently the only drug available to treat schistosomiasis. Since drug resistance... more 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 (IC50s 0.4-20.2μM) and adult schistosomes (IC50s 1.8-22.8μM). Tetraoxanes showed higher cytotoxicity than antischist...
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Papers by Alexander Terent'ev