Novikov, Mikhail Sergeevich

Galenko E.E., Bodunov V.A., Taishev A.E., Novikov M.S., Khlebnikov A.F.

Ilkin V.G., Gridnev I.D., Novikov M.S., Silaichev P.S., Beryozkina T.V., Slepukhin P.A., Dehaen W., Bakulev V.A.

Agafonova A.V., Novikov M.S., Khlebnikov A.F.

Methods for the preparation of 3-aryl-2H-azirine-2,2-dicarboxylic acids and their amides, esters, and azides by FeCl2-catalyzed isomerization of 3-aryl-5-chloroisoxazole-4-carbonyl chlorides into 3-aryl-2H-azirine-2,2-dicarbonyl dichlorides followed by their reaction with nucleophiles are reported. Two approaches to the preparation of 3-aryl-5-chloroisoxazole-4-carbonyl chlorides have been developed.

Golubev A.A., Simdianov I.V., Smetanin I.A., Agafonova A.V., Rostovskii N.V., Khlebnikov A.F., Novikov M.S.

The cascade SN2′ substitution of bromine in alkyl 2-bromo-2H-azirine-2 carboxylates is an efficient method for the preparation of stable 2-azidoazirines, which can be used for the synthesis of 1-(azirin-2-yl)-1,2,3-triazoles by click chemistry.

Prokop’eva I.N., Tomashenko O.A., Matveeva D.R., Galenko E.E., Novikov M.S., Khlebnikov A.F.

Sakharov P., Koronatov A., Khlebnikov A., Petrovskii S., Luginin M., Grachova E., Novikov M.

AbstractTrimethyl phosphite promotes the synthesis of 2,4,5‐trisubstituted 2H‐1,2,3‐triazoles. The protocol developed affords a two‐step method towards triazoles from available reagents. 3,4‐Disubstituted isoxazolones are initially coupled with diazonium tetrafluoroborates. The subsequent reaction is triggered by a single electron transfer from the phosphite to the diazenylisoxazolone under heating or blue LED irradiation at room temperature. The radical anion cascade proceeds via a ring opening/decarboxylation/cyclization sequence. The synthesized triazoles show promising fluorescence in the region from 340 nm to 450 nm with a quantum yield up to 81.6%. The emission energy depends slightly on the substituent nature at the triazole carbon atoms. If an electron‐donor group is introduced into the N2 substituent of the triazole ring, it results in a bathochromic shift of the luminescence energy.

Filippov I.P., Zakharov T.N., Grishin A.V., Khlebnikov A.F., Novikov M.S., Rostovskii N.V.

Titov G.D., Bunev A.S., Urusova S.V., Novikov M.S., Khlebnikov A.F., Rostovskii N.V.

Charushin Valery N., Verbitskiy Egor V., Chupakhin Oleg N., Vorobyeva Daria V., Gribanov Pavel S., Osipov Sergey N., Ivanov Andrey V., Martynovskaya Svetlana V., Sagitova Elena F., Dyachenko Vladimir D., Dyachenko Ivan V., Krivokolysko Sergey G., Dotsenko Viktor V., Aksenov Aleksandr V., Aksenov Dmitrii A., et. al.

The chemistry of heterocyclic compounds has traditionally been and remains a bright area of chemical science in Russia. This is due to the fact that many heterocycles find the widest application. These compounds are the key structural fragments of most drugs, plant protection agents. Many natural compounds are also derivatives of heterocycles. At present, more than half of the hundreds of millions of known chemical compounds are heterocycles. This collective review is devoted to the achievements of Russian chemists in this field over the last 15–20 years. The review presents the achievements of leading heterocyclists representing both RAS institutes and university science. It is worth noting the wide scope of the review, both in terms of the geography of author teams, covering the whole of our large country, and in terms of the diversity of research areas. Practically all major types of heterocycles are represented in the review. The special attention is focused on the practical applications of heterocycles in the design of new drugs and biologically active compounds, high-energy molecules, materials for organic electronics and photovoltaics, new ligands for coordination chemistry, and many other rapidly developing areas. These practical advances would not be possible without the development of new fundamental transformations in heterocyclic chemistry.The bibliography includes 2237 references.

Zanakhov T.O., Galenko E.E., Novikov M.S., Khlebnikov A.F.

Pavlenko J.I., Agafonova A.V., Sakharov P.A., Smetanin I.A., Khlebnikov A.F., Kryukova M.A., Novikov M.S.

Galenko E.E., Novikov M.S., Bunev A.S., Khlebnikov A.F.

Easy-to-handle N-hydroxyacridinecarbimidoyl chloride hydrochlorides were synthesized as convenient nitrile oxide precursors in the preparation of 3-(acridin-9/2-yl)isoxazole derivatives via 1,3-dipolar cycloaddition with terminal alkynes, 1,1-dichloroethene, and acrylonitrile. Azirines with an acridin-9/2-yl substituent attached directly or via the 1,2,3-triazole linker to the azirine C2 were also synthesized. The three-membered rings of the acridine–azirine hybrids were found to be resistant to irradiation in the UV/visible boundary region, despite their long-wave absorption at 320–420 nm, indicating that the acridine moiety cannot be used as an antenna to transfer light energy to generate nitrile ylides from azirines for photoclick cycloaddition. The acridine–isoxazole hybrids linked at the C9–C3 or C2–C3 atoms under blue light irradiation underwent the addition of such hydrogen donor solvents, such as, toluene, o-xylene, mesitylene, 4-chlorotoluene, THF, 1,4-dioxane, or methyl tert-butyl ether (MTBE), to the acridine system to give the corresponding 9-substituted acridanes in good yields. The synthesized acridine–azirine, acridine–isoxazole, and acridane–isoxazole hybrids exhibited cytotoxicity toward both all tested cancer cell lines (HCT 116, MCF7, and A704) and normal cells (WI-26 VA4).

Agafonova A.V., Golubev A.A., Smetanin I.A., Khlebnikov A.F., Spiridonova D.V., Novikov M.S.

Zanakhov T.O., Galenko E.E., Novikov M.S., Khlebnikov A.F.

Novikov M.S., Paramonova M.P., Kirillov I.M., Smirnova O.A., Khandazhinskaya A.L., Chizhov A.O., Kochetkov S.N., Ivanov A.V., Fedyakina I.F.

New title uracil derivatives, 4-{3-[2,6-dioxo-3-(4-aryl-oxybenzyl)-3,6-dihydropyrimidin-1(2H)-yl]propoxy}benzoic acids and their butoxy homologues, were obtained in three steps using 2,4-bis(trimethylsilyloxy)pyrimidine, 4-aryloxy-benzyl bromides and methyl 4-(ω-bromoalkoxy)benzoates as the key reactants. The compounds were studied as inhibitors of H1N1 influenza virus and SARS-CoV-2 R replication in MDCK and Vero E6 cell cultures, respectively, which revealed that the tested compounds had high levels of anti-SARS-CoV-2 activity.

Farivar M., Peirow R., Iraji A., Mahdavi M.

Ribeiro dos Anjos L., Saraiva de Souza J.M., Souza dos Santos A.L., Fabisikova A., Klemm-Abraham M., Zehl M., Antonio da Franca Rodrigues K., Perez Gonzalez E.R.

Zagidullin A.A., Naileva F.F., Fayzullin R.R., Islamov D.R., Miluykov V.A.

Yin Z., Zhang Z., Fu Y., Cui Y.

Polyakov V.S., Pervakova E.V., Grishin Y.K., Beloglazkina E.K.

Durova E.V., Galenko E.E., Shtyrov A.A., Ryazantsev M.N., Kisel K.S., Shakirova J.R., Tunik S.P.

Sarkar R., De Joarder D., Mukhopadhyay C.

Pordel M., Gheibi H., Eftekhari D.J.

Xiong D., Zhang S., Li Z., Yao H., Li L., Huang N., Wang N.

Liu S., Zhou J., Yu L., Liu Y., Huang Y., Ouyang Y., Liu G., Xu X., Shibata N.

Martelli L.S., Furniel L.G., Santiago P.H., Ellena J., Corrêa A.G.

Golmohammadi F., Osmani C., Rominger F., Balalaie S.

Reheim M.A., Abdou M.M., El-Gaby M.S., Al-Omari M.H., Abu-Rayyan A., Al-Assy W.H., Refat H.M., Sarhan A.A., Hafiz I.S.

Abstract Among the foremost goals for organic chemists is to discover novel approaches for the synthesis of a particular heterocyclic and its design. Our approach focused on the vital precursor 4-acetyl-3-phenylisoxazol-5(4H)-one 3, as this molecule has an endocyclic carbonyl function in position 5 adjacent to the substituted acetyl function at site 4. Therefore, compound 3 was a crucial component of many types of fused isoxazole. The investigators provide a straightforward synthesis of fused isoxazole from the following categories: pyrano[3,2-d]isoxazole 4 & 6, isochromeno[4,3-d]isoxazole 5, isoxazolo[4',5':5,6]pyrano[3,4-c]pyridine 7, thieno[3',4':4,5]pyrano [3,2-d]isoxazole 8, pyrazolo[4,3-d]isoxazole 10a,b and 11a,b, and isoxazolo[4,5-c]pyridazine derivatives 14a,b. The target compounds and their structures were supported by the results of 1H-NMR, IR and mass spectroscopy. Molecular docking studies highlighted strong binding affinities to bacterial enzymes crucial for cell wall synthesis, while DFT calculations provided deep insights into their electronic properties and stability. Additionally, the antioxidant potential of compounds 11a,b was assessed using DPPH and ABTS assays, showing impressive concentration-dependent activity. Addressing the critical issue of antibiotic resistance, especially due to β-lactamases, molecular docking affirmed the high binding propensity of these derivatives with essential β-lactamase proteins (PDB: 1CK3, 6MU9, and 6W2Z). These findings underscore the promise of isoxazoline derivatives as powerful antimicrobial and antioxidant agents, paving the way for further development in combating bacterial resistance and oxidative stress.

Petti A., Karrasch M.J., Chahar P., Wessels F.H., Hölter N., Boser F., Daniliuc C.G., Glorius F.

Zhang X., Jiang B., Yang Y., Dong R., Ding J., Miao Z.

AbstractA novel Pd(0)/Au(I) relay catalysis strategy for converting propargylic cyclic carbonates into furans is reported. The method capitalizes on the sequential transformation of a palladium‐stabilized alkoxide‐π‐allyl intermediate into a gold‐stabilized dihydrofuran species, enabled by the cooperative action of palladium and gold catalysts. This approach is notable for its simplicity, broad functional group compatibility, and use of readily available substrates. By extending the methodology to five‐membered carbamates substrates, the construction of pyrrole frameworks is also demonstrated. Additionally, the method facilitates the synthesis of polycyclic furans and pyrroles via Diels‐Alder reactions, achieving high yields with excellent diastereoselectivities.

Prokop’eva I.N., Tomashenko O.A., Matveeva D.R., Galenko E.E., Novikov M.S., Khlebnikov A.F.

Charushin Valery N., Verbitskiy Egor V., Chupakhin Oleg N., Vorobyeva Daria V., Gribanov Pavel S., Osipov Sergey N., Ivanov Andrey V., Martynovskaya Svetlana V., Sagitova Elena F., Dyachenko Vladimir D., Dyachenko Ivan V., Krivokolysko Sergey G., Dotsenko Viktor V., Aksenov Aleksandr V., Aksenov Dmitrii A., et. al.

The chemistry of heterocyclic compounds has traditionally been and remains a bright area of chemical science in Russia. This is due to the fact that many heterocycles find the widest application. These compounds are the key structural fragments of most drugs, plant protection agents. Many natural compounds are also derivatives of heterocycles. At present, more than half of the hundreds of millions of known chemical compounds are heterocycles. This collective review is devoted to the achievements of Russian chemists in this field over the last 15–20 years. The review presents the achievements of leading heterocyclists representing both RAS institutes and university science. It is worth noting the wide scope of the review, both in terms of the geography of author teams, covering the whole of our large country, and in terms of the diversity of research areas. Practically all major types of heterocycles are represented in the review. The special attention is focused on the practical applications of heterocycles in the design of new drugs and biologically active compounds, high-energy molecules, materials for organic electronics and photovoltaics, new ligands for coordination chemistry, and many other rapidly developing areas. These practical advances would not be possible without the development of new fundamental transformations in heterocyclic chemistry.The bibliography includes 2237 references.

Zanakhov T.O., Galenko E.E., Novikov M.S., Khlebnikov A.F.

Dmitrienko A.A., Kroitor A.P., Bunin D.A., Arakcheev A.V., Martynov A.G., Selektor S.L., Tsivadze A.Y., Gorbunova Y.G.

Gudkova I.O., Sorokina E.A., Zaborin E.A., Polinskaya M.S., Borshchev O.V., Ponomarenko S.A.

Mono- and dioctyl-substituted benzo[b]benzo[4,5]thieno[2,3-d]thiophenes C8-BTBT and C8-BTBT-C8 that are widely used as organic semiconductors in the manufacture of various organic electronic devices have been synthesized in two steps, by Friedel–Crafts acylation of benzo[b]benzo[4,5]thieno[2,3-d]­thiophene (BTBT) and subsequent reduction of the ketone group(s). Taking into account that the limiting stage in the synthesis of such compounds is the reduction stage, different methods for the reduction acyl-substituted BTBT derivatives have been studied and probable reduction mechanisms have been proposed. The best results in the keto group reduction stage have been obtained with the use of hydrazine hydrate as reducing agent.

Safonova E.A., Polovkova M.A., Kolomeychuk F.M., Akasov R.A., Savelyev A.G., Khaydukov E.V., Tsivadze A.Y., Gorbunova Y.G.

The search for novel water soluble red and near-IR photoinitiators for biomedical applications is a very important task. Here we describe the synthesis and photophysical properties of a water soluble complex of P(V) with tetra-15-crown-5-phthalocyanine bearing diethylene glycol monoethyl ether as axial ligand (15C5PcP-gly). In addition to intense near-IR absorption, compound 15C5PcP-gly is characterized by a high quantum yield of singlet oxygen generation with moderate photostability. The combination of these properties with the discovered low dark and light induced cytotoxicity and negligible intracellular accumulation makes the complex 15C5PcP-gly promising for biophotopolymerization. Taking advantage of all the benefits of the 15C5PcP-gly complex, we demonstrate for the first time its successful application in the bulk photocuring of a water-soluble polyethylene glycol diacrylate-based system with simultaneous preservation of mammalian cells viability.

Zhu Y., Zhao H., Li Q., Fang B., Wang Y., Qi G.

AbstractThe domino annulation reactions of o‐aminotrifluoroacetophenone derivatives and MBH carbonates enabled by PPh3 have been reported, which provide a series of tetrahydrofuro[3,2‐b]indolines containing a CF3‐substituted tetrasubstituted carbon stereocenters in yields of 74 to 95% and >20:1 dr. In this process, MBH carbonates were used as C1/C3 synthons. The MTT assay shows that the products exhibit the activity of inhibitory effect on proliferation on Hela cancer cell line.

de Sena Murteira Pinheiro P., Franco L.S., Montagnoli T.L., Fraga C.A.

Efimova I.A., Safonova E.A., Polovkova M.A., Martynov A.G., Kirakosyan G.A., Tsivadze A.Y., Gorbunova Y.G.

Water-soluble phosphorus(v) porphyrin with p-amino- phenoxy groups as axial ligands was obtained, and its photophysical and photochemical properties were investigated and rationalized using quantum chemical calculations. It was demonstrated that at pH ≥ 6.1 this porphyrin did not emit or generate singlet oxygen, whereas at pH ≤ 2.0 it completely converted into the N-protonated form, which exhibited fluorescence and the ability to generate singlet oxygen.

Levkov L.L., Borshchev O.V., Pisarev S.A., Fedorov Y.V., Svidchenko E.A., Surin N.M., Ponomarenko S.A.

Synthesis and examination of two highly luminescent oligophenylene derivatives of 2,1,3-benzothiadiazole with branching centers based on benzene-1,3,5-triyl units are described. These studies in combination with DFT calculations have shown that the presence of the branching centers causes differences in the absorption characteristics and similarity of the emission properties. High molar extinction coefficients (up to 15 × 104 dm3 mol−1 cm−1) in the medium UV-range and blue-green emission with quantum yields of 79–93% make them promising components of wavelength-shifting materials for optical devices.

Taylor R.J., Unsworth W.P.

This review concentrates on our research into the discovery of novel ynone-based dearomative spirocyclisation processes, whilst placing the new chemistry into the context of existing knowledge. The genesis of the research programme, the development of efficient synthetic routes to prepare the novel natural products spirobacillene A (1) and spirobacillene B (2), utilised the dearomative spirocyclisation of indole ynones. This stimulated a much wider study to explore the reactivity of ynones in dearomative spirocyclisation processes more generally. Routes to generate a wide range of spirocycles were subsequently developed, with dearomative reactions of ynones tethered to indoles, benzofurans, benzisoxazoles, pyrroles, pyridines, isoquinolines, pyrazines, cyclic ketimines, and anisoles all discussed herein, with these reactions initiated by catalytic Ag(I), Cu(II), Pd(0), photolysis and many other reagents. Asymmetric variants of some of the reactions are also discussed, as is further elaboration of the spirocyclic products to give carbazoles, quinolones, polycycles and other useful synthetic building blocks. Finally, applications of the new methodology in natural product synthesis (e.g. spirobacillene A, lasubine II and indolizidine 209D) are described.

Kroitor A.P., Sinelshchikova A.A., Grigoriev M.S., Kirakosyan G.A., Martynov A.G., Gorbunova Y.G., Sorokin A.B.

We report design and synthesis of novel picket fence phthalocyanines to access the ruthenium(II) complexes carrying di-(1R,2S,5R)-menthoxy -substituted aryloxy-groups. Owing to bulkiness of such groups located either at peripheral (β) or non-peripheral (α) positions, they are nearly orthogonal to the plane of the phthalocyanine thus creating a chiral environment around the metal center. This orthogonality was supported by X-ray analysis of corresponding phthalonitrile precursors (86.0° and 81.4° angles between the planes of aromatic moieties for α- and β-substituted phthalonitriles, respectively). As a proof of concept, the synthesized complexes were investigated as catalysts in a benchmark reaction of the cyclopropanation of styrene by ethyl diazoacetate. While the β-substituted complex showed very low enantioselectivity, the α-substituted analogue afforded a moderate asymmetric induction towards ethyl (1S,2R)-2-phenylcyclopropane-1-carboxylate. This result emphasizes the importance of appropriate arrangement of the chiral groups relative to the phthalocyanine catalytic center and provides guidelines for further elaboration of phthalocyanine catalysts for asymmetric transfer of carbenes.

Ilkin V., Filimonov V., Utepova I.A., Beryozkina T., Slepukhin P.A., Tumashov A., Dehaen W., Bakulev V.A.

A Rh(II)/Cu(I)-catalyzed [4+1]-annulation of readily available thioamides with 1-sulfonyl-1,2,3-triazoles and diazoamides was developed, delivering a general approach toward highly substituted dihydrothiophenes. A series of dihydrothiophenes having a wide diversity of...

Xu F., Zeng F., Luo W., Zhang S., Huo J., Li Y.

Abstract2H‐arizines are important three‐membered heterocycles in organic chemistry. Recently, many advances in the synthesis and functionalization of 2H‐arizines have been reported. Neber rearrangement, isomerization of isoxazole, oxidation of enamine, C−H bond activation, decomposition of vinyl azide, functionalization of alkyne, and multi‐step synthesis have been developed for the efficient assembly of 2H‐azirines. As versatile and highly strained three‐membered unsaturated heterocycles, 2H‐azirines can be used as distinctive building blocks towards significant functional groups, and have attracted extensive attention for the fabrication of numerous heterocycles. Recent studies have focused on [3+n] ring‐expansion reactions, nucleophilic addition of C=N double bond or continuous nucleophilic addition followed by cyclization, ring‐opening of 2H‐azirines to acyclic compounds, and substitution of sp3‐C−H of 2H‐azirines. One of the most critical challenges is seeking for a selective opening of the specific three bonds of the strained azirine circle, some of what can be achieved on the basis of metal catalyst, photocatalysis, or combination of metal catalyst and photocatalysis. In this review, recent advances involving the synthesis and reactivity of 2H‐arizines accompanied with challenges and breakthroughs are summarized. The review mainly covers the period from 2019 to 2023.

Zlotin Sergei G., Egorova Ksenia S., Ananikov Valentine P., Akulov Alexey A., Varaksin Mikhail V., Chupakhin Oleg N., Charushin Valery N., Bryliakov Konstantin P., Averin Alexey D., Beletskaya Irina P., Dolengovski Egor L., Budnikova Yulia H., Sinyashin Oleg G., Gafurov Zufar N., Kantyukov Artyom O., et. al.

After the appearance of the green chemistry concept, which was introduced in the chemistry vocabulary in the early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form the basis for an ideal chemical process. This review analyzes the accumulated experience and achievements towards the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. The review presents the views of leading Russian scientists specializing in various fields of this subject, including homogeneous and heterogeneous catalysis, fine and basic organic synthesis, electrochemistry, polymer chemistry, chemistry based on bio-renewable feedstocks and chemistry of energetic compounds and materials. A new approach to the quantitative evaluation of the environmental friendliness of processes developed by Russian authors is described.The bibliography includes 1761.