Leonid Fershtat

Leonid Fershtat
N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences

PhD Dr.Sci. in Organic Chemistry

About

78
Publications
5,595
Reads
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1,045
Citations
Additional affiliations
June 2015 - present
N. D. Zelinsky Institute of Organic Chemistry
Position
  • Senior Researcher
September 2007 - present
Russian Academy of Sciences
Position
  • Researcher
Education
September 2012 - June 2015
N. D. Zelinsky Institute of Organic Chemistry
Field of study
  • Organic chemistry
September 2007 - June 2012

Publications

Publications (78)
Article
Full-text available
Several energy-rich bifuroxans incorporating nitro and azido functionalities have been synthesized and thoroughly characterized by IR and multinuclear NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction and differential scanning calorimetry. N-oxide regiochemistry was employed to design the tunable azido(nitro)bifuroxans with dif...
Article
This review covers synthesis and performance of the most prospective 1,2,5‐oxadiazole‐based high‐energy density materials (HEDMs). These materials comprise of a 1,2,5‐oxadiazole subunit as a key structural motif linked to various acyclic explosophoric groups or to nitrogen‐rich and nitrogen‐oxygen azoles: 1,2,4‐triazole, tetrazole, 1,2,4‐ and 1,3,4...
Article
A novel one‐pot cascade method for the assembly of valuable NO‐donor azasydnone scaffold has been developed. This construction strategy involves a diazotization/azo coupling/elimination/double rearrangement cascade sequence of readily available amines. The current protocol enables the generation of a diverse array of azasydnones, including previous...
Article
A series of highly energetic organic salts comprising of a tetrazolylfuroxan anion, explosophoric azido or azo functionalities and nitrogen‐rich cations was synthesized by simple, efficient and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N, 15N) spectroscopy, elemental analysis...
Article
A new approach to the hetaryl carbamates through the tandem condensation/rearrangement reaction of 2‐aminohetarene N‐oxides was developed. The discovered reaction is suitable for both five‐ and six‐membered heterocycles and proceeds through the condensation of 2‐aminohetarene N‐oxide with trimethyl orthoformate followed by intramolecular N‐oxide ox...
Article
The review presents the general methods for the formation of the framework of 1,4-dihydro- 1,2,4-benzotriazin-4-yl radicals (Blatter radicals) and their polycyclic derivatives published over the past 7 years. The target heterocyclic structures are formed by a number of approaches such as oxidative cyclization of amidrazones, addition of organolithi...
Article
Full-text available
A series of novel 1,4-dihydrobenzo[1,2,4][e]triazines bearing an acetyl or ester moiety as a functional group at the C(3) atom of the 1,2,4-triazine ring were synthesized. The synthetic protocol is based on an oxidative cyclization of functionally substituted amidrazones in the presence of DBU and Pd/C. It was found that the developed approach is s...
Article
A method for the introduction of the N,N-dimethylformamidine protective group in a series of six-membered 2-aminohetarene N-oxides was developed. It was shown that 2-amino derivatives of N-oxides of various six-membered heterocycles (pyridines, pyrimidines, pyrazines, tetrazines) successfully enter the reaction. The stability of the N,N-dimethylfor...
Article
A series of novel, structurally diverse 1,2,4- and 1,2,5-oxadi- azole assemblies was synthesized from readily available furoxanyl precursors. Experimentally determined physico-chemical properties and calculated detonation parameters showed an application potential of the prepared nitrogen-oxygen molecular systems as promising energetic materials.
Article
Full-text available
Furoxan derivatives enriched with explosophoric functionalities are promising compounds in the preparation of novel energetic materials. Herein, a previously unknown potassium (3-methyl-2-oxido-1,2,5-oxadiazol-4-yl)dinitromethanide (also referred to as potassium 4-dinitromethyl-3-methylfuroxanate) was synthesized via tandem nitration-reduction reac...
Article
Analysis of thermal behavior of liquids is often accompanied by vaporization. In an extreme case, the calorimetric (DSC) experiment reveals the only endothermic evaporation instead of the more valuable thermal decomposition. 3-Methylfuroxan (MMF) is an energetic monosubstituted 1,2,5-oxadiazole N-oxide that shows the above behavior. We investigate...
Article
A general method for the synthesis of a series of previously unknown N-(heteroaryl)- and N-(aryl)aminotetrazoles through the tandem electrocyclization/hydrolysis of azidohydrazones was accomplished. The described protocol was suitable for a wide array of the target N-substituted aminotetrazoles which were prepared in good to high yields under smoot...
Article
Novel efficient synthetic strategies, including green methodologies, to basic and perspective high-energy density compounds, bearing active oxygen sources (C-, N- and O-nitro groups and N-oxide fragments) and high-enthalpy polynitrogen heterocycles, are briefly overviewed. Recently developed synthetic approaches to nitro group-free hypergolic ionic...
Article
Mechanical and thermal hazards are critical for chemical compounds. Foremost, the design of novel energetic materials that are stable, insensitive, but have a detonation performance superior to in-service materials is of great interest. However, a single source of safety data for hazardous materials with explosophoric functionalities is still missi...
Article
Full-text available
Nitric oxide (NO) is a key signaling molecule that acts in various physiological processes such as cellular metabolism, vasodilation and transmission of nerve impulses. A wide number of vascular diseases as well as various immune and neurodegenerative disorders were found to be directly associated with a disruption of NO production in living organi...
Article
Full-text available
A series of highly energetic nitrogen-rich salts comprised of a 5-(trinitromethyl)tetrazolate anion and high-nitrogen cations was synthesized by simple and efficient chemical routes from readily available commercial reagents. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, elemental analysi...
Article
A regioselective method for an assembly of pharmacologically relevant fully substituted furoxans and isoxazoles using the ring distortion diversity-oriented approach through the one-pot ring cleavage/nucleophilic addition/oxidation cascade of monosubstituted furoxans was developed. The described synthetic strategy is highly regioselective and provi...
Article
A series of biheterocyclic assemblies comprising of 1,2,5‐oxadiazole and azasydnone scaffolds were synthesized and biologically evaluated as novel NO‐donor and antiplatelet agents. Depending on functional substituents at the biheterocyclic core, all studied compounds demonstrated good NO‐donor profiles releasing NO in a wide range of concentrations...
Article
A series of novel energetic materials comprising of azo‐bridged furoxanylazoles enriched with energetic functionalities was designed and synthesized. These high‐energy materials were thoroughly characterized by IR and multinuclear NMR ( 1 H, 13 C, 14 N) spectroscopy, high‐resolution mass spectrometry, elemental analysis, and differential scanning c...
Article
Five-membered heterocyclic N-oxides attract special attention due to their significant potential applications in medicinal chemistry and advanced materials science. In this regard, novel methods for their synthesis and functionalization are in constant demand. In this short review, recent state-of-the-art achievements in the chemistry of isoxazolin...
Article
Using quantum chemical methods and the original technique based on atom-atom potential methods, the molecular and crystal structure simulation of all possible structural forms of nitrodiaziridines were carried out. The possible pathways of thermal decomposition of nitrodiaziridines were modeled, and the most stable forms were identified. Thermodyna...
Article
Full-text available
In recent years, the development of novel advanced high-energy density materials has significantly shifted toward nitrogen-containing heterocyclic derivatives, which demonstrate a great potential for multipurpose application patterns. Among known heterocycles hydroxytetrazole is of special importance due to its high nitrogen-oxygen content and a po...
Article
A simple and effective protocol for the synthesis of 2H-pyrazolo[3,4-d]pyridazine 5,6-dioxides includes a transformation of accessible 3,4-diacetyl-5-methyl-1H-pyrazoles into the corresponding 1,4-dioximes followed by their N2O4- mediated oxidative cyclization. All transformations proceed under mild conditions in good to high yields. According to t...
Article
Full-text available
In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalp...
Article
A straightforward synthesis of a series of previously unknown N-(1,2,5-oxadiazolyl)hydrazones through the diazotization/reduction/condensation cascade of amino-1,2,5-oxadiazoles was accomplished. The described protocol was suitable for a wide array of target hydrazones, which were prepared in good to high yields under smooth reaction conditions wit...
Article
The Front Cover illustrates the ability of arylazofuroxans to switch between two isomers, a process easily tuned by visible light or elevated temperature, and which significantly affects NO‐donor ability. More information can be found in the Article by Leonid L. Fershtat and co‐workers.
Article
The front cover artwork is provided by the Laboratory of Nitrogen‐Containing Compounds at the Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences (ZIOC RAS; Russia). The image shows a metronome which symbolizes the ability of arylazofuroxans to switch between two isomers with significantly different NO donor ability. The swit...
Article
A series of novel molecular photoswitches incorporating an aryldiazenyl moiety linked to the 1,2,5‐oxadiazole (furazan) or 1,2,5‐oxadiazole 2‐oxide (furoxan) subunit was synthesized by a simple and step‐economy chemical route. Upon visible light irradiation ( E )‐arylazo‐1,2,5‐oxadiazoles underwent photoisomerization to the corresponding ( Z )‐isom...
Article
The equilibrium molecular structures of the isomeric 3-methyl-4-nitro- and 4-methyl-3-nitrofuroxans have been determined for the first time by gas-phase electron diffraction (GED) supported by coupled cluster calculations up to CCSD(T)/cc-pVTZ level of theory, in frame of dynamic model with relaxation of all structural parameters. The best fit of t...
Article
A tandem method of synthesis of 3-hetaryl-4-nitrofuroxans was developed based on the one-pot sequence of thermolysis of 4-nitrofuroxannitrolic acid to the corresponding 4-nitro-3-furoxancarbonitrile oxide and [3+2] cycloaddition of the latter to acetylenes and olefins. It was established that the synthesized 3-(isoxazol-3-yl)- and 3-(isoxazolin-3-y...
Article
A novel method for the synthesis of a diverse series of functionally substituted five-membered heterocyclic compounds via atom-economic, regio-, and diastereoselective one-pot reaction cascade was developed. This approach involves a ring opening in 4-arylfuroxans to α-oximinoarylacetonitrile oxides followed by [3+2] cycloaddition to various dipolar...
Article
A novel one-pot approach for the synthesis of 1,2,4- and 1,2,5-oxadiazole ring assemblies has been developed. The synthetic strategy involves the condensation of furoxanyl amidoximes with aldehydes and subsequent iodine-mediated oxidation of the intermediate 1,2,4-oxadiazolines. The analogous reaction of 4-aminofuroxanyl-3-carboxamidoxime results n...
Chapter
1,2,5-Oxadiazoles (furazans) and 1,2,5-oxadiazole 2-oxides (furoxans) as well as their benzannulated derivatives (benzo[c][1,2,5]oxadiazoles and benzo[c][1,2,5]oxadiazole 1-oxides) are a widely known subclass of heterocycles. 1,2,5-Oxadiazoles exhibit a unique set of properties that has led to their use in the design of pharmacologically active and...
Article
In this review article, we provide general information on the known methods for directed synthesis of 3- and 4-aminofuroxans, as well as analyze the main aspects of their reactivity. Methods for regio- and chemoselective transformations of aminofuroxans are considered in detail, including both classical reactions involving oxidation, acylation, and...
Article
Full-text available
Crystallization of different biological targets and pharmaceuticals from ionic liquids (ILs) could result in previously unknown polymorph modifications. Crystallization of high energy materials (HEMs) from ILs has not been studied so far. This paper is devoted to the first attempts to crystallize a highly energetic compound – 2,4,6,8,10,12-hexanitr...
Article
A new approach for the synthesis and reactivity of the 1,2,5‐oxadiazolyl diazonium salts is represented. A simple and direct protocol to previously inaccessible furoxanyl and furazanyl diazonium salts was developed for the first time. Azo coupling reactions of thus obtained diazonium salts with a series of structurally diverse CH‐acids have been al...
Article
Hetarylfuroxans (4-(2-methylpyridin-5-yloxy)-3-phenylfuroxan (1), bis(1,2,4-oxadiazol- 3-yl)furoxan (2), and 4-amino-3-(indenotriazin-3-yl)furoxan (3)) exhibit in vitro cytotoxic activity against chronic myeloid leukemia K562 cells. All studied furoxans induce apoptosis in K562 cells. The experiments with activation of caspases-3 and -7 showed that...
Article
A series of functionalized furoxans was synthesized, and their effect on the platelet aggregation was estimated using a set of inducers. New hybrid structures comprising the furoxan ring and glycolic or acetylsalicylic acid motifs effectively inhibit aggregate formation induced by adenosine diphosphate and adrenaline. Studies of their NO-donor abil...
Article
The effective and regioselective synthesis of new (2-hydrazinylthiazol-4-yl)furoxan hydrobromides based on the condensation of (bromoacetyl)furoxans with thiosemicarbazide has been developed. The cytotoxic activity of their derivatives (with hydrazone, 4-thiazolo[2.3-c][1,2,4]triazole or pyrrole moieties) against two human cancer cell lines (A549,...
Article
A facile and chemoselective SnCl2-mediated mild reduction of regioisomeric 3- and 4-nitrofuroxans for the synthesis of amino­furazans and aminofuroxans in good yields is developed. Reduction of 4-nitrofuroxans results in the selective formation of 4-aminofuroxans, while analogous reduction of 3-nitrofuroxans affords 3-aminofurazans as a result of s...
Article
A new eco-friendly synthesis of azofuroxans comprises the oxidative N–N coupling of aminofuroxans under the action of electrogenerated NaOCl and NaOBr. In addition, an oxidative isomerization of the aminofuroxan motif was found for the first time, which resulted in a formation of unsymmetrical azofuroxans.
Article
[Figure not available: see fulltext.] A highly effective method for the preparation of 7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines was developed on the basis of condensation reaction between aryl(hetaryl) α-bromo ketones and commercially available thiocarbohydrazide, followed by treatment of the obtained 2-hydrazinyl-6H-1,3,4-thiadiazine hydrobromi...
Article
Full-text available
The nitramino derivatives of furoxans are of specific interest as precursors for the preparation of high energy salts with nitrogen-rich cations. In this communication, the 3,3′-(diazene-1,2-diyl)bis[4-(nitroamino)-1,2,5-oxadiazole 2-oxide] was prepared via nitration of available 4,4′-diamino-3,3′-diazenofuroxan; the best yield of the target compou...
Article
Among the variety of nitrogen heterocycles, the furoxan (1,2,5-oxadiazole 2-oxide) scaffold has attracted considerable attention owing to its ability to release NO under physiological conditions. Therefore, significant efforts of organic chemists have been directed toward the construction of new drug candidates containing the NO-donor furoxan subun...
Article
The effect of the water-soluble furoxan derivatives on platelet aggregation has been estimated using a series of inducers. The most active compound, 3-carbamoyl-4-(hydroxymethyl)furoxan (CAS-1609), effectively inhibits aggregate formation induced by adenosine diphosphate and adrenaline. This result is a good basis for the search of new structures w...
Article
A highly efficient, safe and sustainable procedure was developed for the synthesis of various pharmacology-relevant and/or energy-rich nitro esters. It is based on nitration of corresponding alcohols with dinitrogen pentoxide in the liquid 1,1,1,2-tetrafluoroethane medium. The proposed approach is attractive for commercial applications because it o...
Article
Full-text available
The design of novel energetic materials with improved performance, optimized parameters, and environmental compatibility remains a challenging task. In this study, new high‐energy materials based on isomeric dinitrobi‐1,2,5‐oxadiazole structures comprising nitrofurazan and nitrofuroxan subunits were synthesized. Due to planarity and strong noncoval...
Article
A simple, general, and regioselective method has been developed for the synthesis of a series of heteroarylfuroxans, including isoxazolyl-, isoxazolinyl- and (1,2,4-oxadiazolyl)furoxans. The described method is based on a cascade of one-pot processes, including the nitration of furoxancarbaldehyde oximes, thermolysis of the formed nitrolic acids to...
Article
A new, simple, and general method for the synthesis of 6-R-7H-tetrazolo[5,1-b][1,3,4]thiadiazines (R = Ar, Het, Alk) has been developed. The described method is based on the one-pot condensation of α-haloketones with thiocarbohydrazide, nitrosation of the formed hydrazinylthiadiazine using NaNO2/HCl, and intramolecular cyclization of the nitrosatio...
Article
Full-text available
A direct approach to the synthesis of previously unknown 1H-1,2,3-triazolylfuroxans, involving nucleophilic substitution of the nitro group in nitrofuroxans followed by catalytic [3+2] cycloaddition of intermediate azidofuroxans to 1,3-ketoesters, is reported. The scope of the triazolylfuroxans was additionally diversified through a number of trans...
Article
A global increase in the environmental pollution demands the development of new "cleaner" chemical processes. Among urgent improvements, replacement of traditional hydrocarbon-derived toxic organic solvents with neoteric solvents less harmful for the environment is one of the most vital issues. Due to favorable combination of unique properties, ion...
Article
Full-text available
Novel regioselective approach to the synthesis of (1H-1,2,3-triazol-1-yl)furoxans based on Lewis acid-catalyzed Wolff cyclocondensation of aminofuroxans with diazo-β-dicarbonyl compounds has been developed. This approach allows to involve aminofuroxans as substrates which are very weak nucleophiles and usually do not participate in reactions with c...
Article
The molecular hybridization of different compounds with known pharmacological activity comes into particular prominence for the design of potential drugs with improved pharmacokinetic profile. Especially great attention in last decade is focused on the synthesis of hybrid structures comprising an NO-donor framework since NO is a ubiquitous and cruc...
Article
The title reaction involves the acylation of the sodium salt (II) of dinitromethan with furoxanyl hydroxamic acid chlorides, nitrosation of the resulting product, and subsequent cyclization by slight increase of temperature.
Article
A general and simple method for the preparation of under explored 3-aryl-4-hydroxyfuroxans by nucleophilic substitution of the nitro group in 3-aryl-4-nitrofuroxans using NaOH in H2O-THF has been developed. The methylation of 3-aryl-4-hydroxyfuroxans was studied with various methylating reagents (CH2N2, MeI, (MeO)2SO2) which showed for the first ti...
Article
This review is concerned with recently developed synthetic methods for non-annelated polynuclear heterocyclic systems that incorporate, along with a furazan and(or) furoxan ring, polynitrogen and nitrogen ± oxygen heterocycles (1,2,4- and 1,3,4- oxadiazole, 1,2,3- and 1,2,4-triazole, tetrazole, pyrazole, sym-triazine, 1,2,4,5-tetrazine and so on) l...
Article
A regioselective method for the synthesis of previously unknown bifuroxanyl systems containing the 3-nitrobifuroxanyl core, based on a cascade of one-pot reactions comprising of the acylation of dinitromethane sodium salt with furoxanyl hydroxamic acid chlorides, nitrosation of the acylation product with NaNO2/AcOH/AcONa, and intramolecular cycliza...
Article
The title methods involve the [4+2] cycloaddition of enamine or norbornadiene to the triazine ring of triazinfuroxans followed by one-pot transformation of the formed intermediates affording a series of polyheterocyclic compounds combining furoxan and pyridine rings in one molecule through a C—C bond.
Article
Two convenient, facile, regioselective and highly effective one-pot protocols for the synthesis of previously unknown hybrid heterocyclic systems with the furoxanylpyridine core based on the tandem inverse-electron-demand hetero-Diels–Alder/retro-Diels–Alder reactions of the tailor-made (1,2,4-triazin-3-yl)furoxans with 1-(pyrrolidino)cyclohexene a...
Article
Full-text available
A general, simple, and effective method has been developed for the preparation of previously practically unknown (5-R-1De-1,2,4-triazol-3-yl)furoxans with various substituents at the other carbon atom of furoxan ring, based on condensation of furoxanylamidrazones with electrophilic reagents (cyanogen bromide, acetic and trifluoroacetic anhydrides).
Article
The [3 + 2] cycloaddition of azidofuroxans to internal and terminal acetylenes was found to occur only in ionic liquids on heating and afford (1H-1,2,3-triazol-1-yl)furoxans in moderate to good yields. The reaction with terminal acetylenes proceeds with high regio- selectivity.
Article
Full-text available
A general, facile, highly effective one-pot protocol for the synthesis of new types of heterocyclic systems incorporating mono- and bis(1,2,4-oxadiazol-3-yl)furoxan cores based on the tandem heterocyclization of furoxanylamidoximes with various aliphatic, aromatic, and heterocyclic carboxylic acid chlorides under very mild conditions (Cs2CO3,MeCN,...
Article
Hetarylthiofuroxans were synthesized by nucleophilic substitution of the nitro group in 4-nitrofuroxans under the action of hetarylthiols in the DBU-MeCN system at room temperature, reactivity of 4-nitrofuroxans being dependent on the C(3)-substituent.
Article
We report a general method for the synthesis of previously unknown heterocyclic systems containing furoxan and heterocyclic fragments linked by S- and О-bridges, based on nucleophilic substitution of nitro group in 4-nitrofuroxans with HetS and HetO groups introduced by reactions with hetarylthiols and hydroxy heterocycles in 1,8-diazabicyclo[5.4.0...
Article
A novel general approach towards various nitroazoles via tandem process involving dinitrofuroxan cycloreversion followed by [3+2] cycloaddition of generated in situ nitroformonitrile oxide is developed. The reaction is promoted by addition of catalytic amounts of ionic liquids. Plausible mechanisms of the described processes based on quantum chemic...
Article
A new, simple and general one-pot method for the preparation of (5-R-1,3,4-oxadiazol-2-yl)furoxans has been developed on the basis of the interaction between accessible 3-methylfuroxan-4-carboxylic acid hydrazide and aliphatic, aromatic and heterocyclic carboxylic acids or their chlorides in the presence of POCl3. The synthesis and study of (5-R-1,...
Article
A new approach to the synthesis of 3-nitroisoxazoles and 3-nitroisoxazolines based on the [3+2]-cycloaddition of nitroformonitrile oxide (NFNO), generated by the cycloreversion of dinitrofuroxan (DNFO), to acetylene and ethylene derivatives, under ionic liquid catalysis is developed. The approach is of a general nature and applicable to cycloadditi...
Article
4-Nitrofuroxans (4-nitro-1,2,5-oxadiazole 2-oxides) were prepared by a dinitrogen trioxide–mediated domino reaction of acrylic acids under the action of NaNO2 excess in AcOH at room temperature. The reaction proceeds completely regioselectively and presents a new, simple, general, and safe method for the preparation of both 3-aryl- and 3-alkyl-4-ni...
Article
An interaction of 1,2-dialkyldiaziridine and 1,2,3-trialkyldiaziridine with methyl propiolate was studied both in organic solvent (MeCN, CH2Cl2, C6H6) and in ionic liquids. Earlier unknown linear structures, in which three molecules of methyl propiolate were suited to one diaziridine molecule (adducts 1 : 3), were obtained in MeCN. The diaziridine...
Article
An interaction of carbonyl compounds (isatins, 4-nitrobenzaldehyde) with azomethine imines generated by the diaziridine ring opening in 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of BF3·Et2O as a catalyst induced the metathesis to other azomethine imines with the elimination of aldehydes ArCHO. New azomethine imines were trapped with die...