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Straightforward Access to the NO-Donor Azasydnone Scaffold by Cascade Reactions of Amines
Chemistry - A European Journal. 2019. Vol. 25. No. 63. P. 14284–14289.
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 previously hardly accessible heteroaryl substituted azasydnones (25 examples, 70-97% yield) with a good functional group tolerance under very mild conditions. Preliminary NO-releasing studies revealed an ability of azasydnones to produce NO in a wide range of concentrations. This method provides a new approach to nitrogen-oxygen heterocycles with potential applications in medicine and material science.
Platonov D., Belyy A., Salikov R. et al., Beilstein Journal of Organic Chemistry 2026 Vol. 22 P. 64–70
A reactivity umpolung approach for the derivatization of cycloheptatrienes was extended to hexa(methoxycarbonyl)cycloheptatriene, which forms the corresponding anion reactive towards electrophiles. Despite the presence of four potential reactive sites, the reactions mainly involve the initial electrophilic attack onto the α-position relative to the hydrogen atom. The selectivity is either due to the high stability of ...
Added: January 9, 2026
Trainov K., Salikov R., Belyy A. et al., Mendeleev Communications 2022 Vol. 32 No. 2 P. 262–264
The configuration of N-[1,2-bis(methoxycarbonyl)vinyl]-pyridinium intermediate generated from stereoisomers of dimethyl dibromosuccinate or dimethyl bromobutenedioate does not depend on the precursors’ configuration, as distinct from the yields and the reaction rates. The use of various nucleophiles in these cascade reactions gives either cycloheptadieneoctacarboxylic or cycloheptatrienehepta-carboxylic esters along with pyridinium 5-dicyano-methylidene-2,3,4-tris(methoxycarbonyl)cyclopenta-1,3-dien-1-olate. In the latter case, the acyclic ‘Diels’ ...
Added: September 27, 2024
Fedorenko A., Ivanova V., Minyaev M. E. et al., ChemistrySelect 2023 Vol. 8 No. 43 Article e202303122
General method for the annulation of [1,2,5]thiadiazole ring to pyridine and benzene cycle has been developed using sulfur monochloride as a sulfur source. On this basis a number of [1,2,5]thiadiazolo[4,3-b]pyridines and benzo[c]thiadiazoles were synthesized. The most π-deficient [1,2,5]thiadiazolo[4,3-b]pyridines readily react with neutral carbon nucleophiles such as CH-acids, indoles, pyrrole and phloroglucinol to give 1,4-adducts. ...
Added: February 14, 2024
Stebletsova I., Alexander A. Larin, Ivan V. Ananyev et al., Molecules 2023 Vol. 28 No. 19 Article 6969
A facile and efficient method for the regioselective [3 + 2] cycloaddition of 4-azidofuroxans to 1-dimethylamino-2-nitroethylene under p-TSA catalysis affording (4-nitro-1,2,3-triazolyl)furoxans was developed. This transformation is believed to proceed via eliminative azide–olefin cycloaddition resulting in its complete regioselectivity. The developed protocol has a broad substrate scope and enables a straightforward assembly of the 4-nitro-1,2,3-triazole motif. Moreover, ...
Added: October 12, 2023
Zhilin E., Ivan V. Ananyev, Pivkina A. et al., Dalton Transactions 2022 Vol. 51 No. 37 P. 14088–14096
Nitrogen-oxygen organic materials constitute an important family of multipurpose high-energy materials. However, the preparation of energetic boosters and oxidizers for various civil and space technologies remains a challenging task and such materials usually require special precautions and fine tunability of their functional properties. To find a balance between energy and safety while retaining the oxidizing ...
Added: October 24, 2022
Fershtat, Leonid L., Teslenko F., Synthesis 2021 Vol. 53 No. 20 P. 3673–3682
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 isoxazoline N-oxides, 1,2,3-triazole 1-oxides and 1,2,5-oxadiazole 2-oxides are summarized. The main ...
Added: September 12, 2022
Чаплыгин D., Gorbunov Y., Leonid L. Fershtat, Asian Journal of Organic Chemistry 2021 Vol. 10 No. 10 P. 2644–2653
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 provides single furoxan regioisomers upon utilization of N- or S-nucleophiles. Utilization of the cyanide-anion as ...
Added: September 12, 2022
Larin A., Shaferov A., Epishina M. et al., ACS Applied Energy Materials 2020 Vol. 3 No. 8 P. 7764–7771
Several energy-rich bifuroxans incorporating nitro and azido functionalities have been synthesized and thoroughly characterized by IR and multinuclear NMR spectroscopy, elemental analyses, single-crystal X-ray diffraction, and differential scanning calorimetry. N-oxide regiochemistry was employed to design the tunable azido(nitro)bifuroxans with different physicochemical and energetic properties. All synthesized compounds have high enthalpies of formation (449-777 kJ mol(-1)) ...
Added: April 12, 2021
Chaplygin D., Ananyev I., Fershtat L. et al., Synthesis 2020 Vol. 52 No. 18 P. 2667–2678
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 alpha-oximinoarylacetonitrile oxides followed by [3+2] cycloaddition to various dipolarophiles to afford multisubstituted isoxazoles and isoxazolines. Subsequent azole-azole rearrangement of (oximino)isoxazolines/-isoxazoles, ...
Added: April 12, 2021
Nifant'ev E., Ivchenko P., Vinogradov A., Coordination Chemistry Reviews 2021 Vol. 426 P. 213515
Metallocenes of the group 4 metals have attracted great attention as precursors of single-site catalysts forthe production of advanced polyolefins. The annelation of a cyclopentadienyl ring with a heterocyclicfragment fundamentally changes the electronic and structural characteristics ofg5-coordinated ligandsand provides new dimensions for the design of novel and effective catalysts. Heterocycle-fused half-sandwich and sandwich metal complexes, ...
Added: November 11, 2020
Anikin O., Leonov N., Klenov M. et al., European Journal of Organic Chemistry 2019 No. 26 P. 4189–4195
7‐Nitro‐3‐(nitro‐NNO‐azoxy)[1,2,4]triazolo[5,1‐c][1,2,4]‐triazin‐4‐amine (4) is the first high‐melting compound bearing adjacent nitro‐NNO‐azoxy and amino groups. It was synthesized by nitration of 7‐nitro‐3‐(tert‐butyl‐NNO‐azoxy)[1,2,4]triazolo[5,1‐c][1,2,4]triazin‐4‐amine (3) with NO2BF4. Compound 4 is a rather thermally stable (decomposition onset temperature 154 °C), highly energetic (calculated heat of formation 580 kcal·kg–1), and highly dense (1.875 g cm–3) material with a CO‐level oxygen balance. ...
Added: October 15, 2020
Ananyev I., Тесленко Ф. Е., Чураков А. et al., Tetrahedron Letters 2020 Vol. 61 No. 13 P. 151678-1–151678-5
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 not only in formation of the 1,2,4-oxadiazole subunit, but also rearrangement of the furoxan ...
Added: August 11, 2020
Ananyev I., Жилин Е., Ферштат Л. et al., European Journal of Organic Chemistry 2019 Vol. 26 P. 4248–4259
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 also successfully performed. Therefore, ...
Added: October 4, 2019