The number of plans and scientific ideas should always be much greater than the possibilities for their implementation, so that there is plenty to choose from; the right choice of the most promising ideas determines the efficiency of work; but if "something goes wrong" during the implementation, one should not get upset: perhaps this "something" is more interesting than the original idea.
Graduated from Moscow State University (field of study – Chemistry).
Defended his thesis on "Three-dimensional reaction diagram as a method for analyzing reactivity in nucleophilic substitution processes".
Was a visiting scientist in Inha University, Incheon, Korea.
Was a member of the methodological commission of the All-Russian Olympiad for schoolchildren in Сhemistry, since 2005 he has been a member of the methodical commission of the Mendeleev Olympiad for schoolchildren, in both Olympiads he supervises the section "Organic Chemistry".
Was awarded the title of Associate Professor at the Department of Organic Chemistry.
Was an expert Methodist in Chemistry at the Center for Gifted Children in Homs, Syria. Since 2010, he has headed the laboratory of chemical synthesis of the Dmitry Rogachev Federal Scientific and Clinical Center for Pediatric Hematology, Oncology and Immunology
Defended his doctoral dissertation on "Furans in the synthesis of azaheterocycles".
- "Theoretical Organic Chemistry"
- "Macromolecular Chemistry"
- "Chemistry of drugs"
- author / co-author of more than 70 articles in scientific journals, more than 70 teaching and methodical works, 8 patents of the Russian Federation and 9 foreign patents, co-author of the monograph " Fullerenes " and chapters in the monograph “Fluorine in Heterocyclic Chemistry”, member of the editorial board of the journal Chemistry of Heterocyclic Compounds . The Hirsch Index 18.
- research grants since 2005:
- 2014-2016 "Activated cyclopropanes as reagents in the synthesis of physiologically active compounds", Grant RNF (head)
- 2014-2016 "Establishment and research of new molecular switch based on the cis- and trans-3 (4) -amino-4 (3) -gidroksipiperidina and trans-3,4-diatsiloksipiperidina, RFFI grant (performer)
- 2013-2015 "Oxidative recyclizations of furans in the synthesis of heterocycles", RFBR grant (performer)
- 2013-2015 "Development of methodological approaches to physiologically active annelated pyrroles based on furan synthetic platform", RFBR grant (performer)
- 2012-2014 "Cyclopropylindoles are novel reagents in the synthesis of polycyclic indole-containing systems. Approaches to the synthesis of indole alkaloids », RFBR grant (performer)
- 2012-2013 "Donor-acceptor-substituted cyclopropanes - promising reagents in the synthesis of carbo- and heterocycles", RFBR grant (performer)
- 2012-2013 "Lewis acid catalyzed reactions of donor-acceptor cyclopropanes in the synthesis of physiologically active compounds", the Federal Program of the Ministry of Education and Science of the Russian Federation (head)
- 2011-2013 "Conformational control and construction of molecular switches based on trans-3,4-dihydroxypiperidines and its analogues", RFBR grant (performer)
- 2010-2012 "Intramolecular transformations of furans catalyzed by acids", RFBR grant (performer)
- 2009-2011 "Donor-acceptor cyclopropanes as ambiphilic reagents in the design of carbo- and heterocyclic systems", RFBR grant (performer)
- 2008-2010 "Directed synthesis of new nanostructures based on two pharmacophore fragments - highly functionalized piperidine and fullerene derivatives", RFBR grant (performer)
- 2007-2009 "Creation and use of fullerene derivatives for production of medical nanoparticles", RFBR grant (performer)
- 2005-2007 "Directed synthesis of new biologically active compounds based on multifunctionalized derivatives of piperidine and decahydro-1,6-naphthyridine. Stereochemistry and antiviral activity ", RFBR grant (performer)
- studying the reactivity of donor-acceptor cyclopropanes;
- the reaction of furan derivative recyclization;
- the use of new reactions found in the synthesis of natural compounds and their structural analogs, and in the search for new physiologically active substances.
Pavlova A.S., Ivanova O.A., Chagarovskiy A.O., Stebunov N.S., Orlov N.V., Shumsky A.N., Budynina E.M., Rybakov V.B., Trushkov I.V.
Domino Staudinger/aza-Wittig/Mannich reaction: An Approach to Diversity of Di- and Tetrahydropyrrole Scaffolds.
Chem. Eur. J. 2016, 22, № 50, 17967-17971.
Abstract: A highly efficient and selective domino reaction producing valuable di- and tetrahydropyrrole-based skeletons from azidoethyl-substituted CH-acids and (thio)carbonyl compounds has been developed. By involving the additional functional groups in starting compounds into the domino reaction or postmodification of the primary reaction products, the simple construction of the pharmaceutically relevant three- and polycyclic azaheterocyclic scaffolds was demonstrated
Makarov A.S., Sorotskaya L. N., Uchuskin M.G., Trushkov I.V.
Synthesis of Quinolines via Acid-Catalyzed Cyclodehydration of 2-(Tosylamino)chalcones
Chemistry of Heterocyclic Compounds. 2016. Т. 52. № 12. С. 1087-1091.
Abstract: The acid-catalyzed cyclodehydration of (E)-3-[(2-tosylamino)phenyl]-1-(het)arylprop-2-en-1-ones to 2-substituted quinolones was investigated. The reaction proceeds via the key step of (E,Z)-isomerization with subsequent intramolecular cyclization affording the target compounds in high yields.
Abaev V.T., Trushkov I.V., Uchuskin M.G.
THE BUTIN REACTION
Chemistry of Heterocyclic Compounds. 2016. Т. 52. № 12. С. 973-995.
Abstract: Acid-catalyzed recyclization of 4-acetoxy-9-furylnaphtho[2,3-b]furans efficiently produced naphtho[1,2-b:3,4-b’]difurans. On the other hand, 4-aminonaphtho[2,3-b]furans failed to undergo the analogous recyclization into benzo[g]furo[2,3-e]indoles. The difference in behavior of these two types of substrates was explained by employing density functional theory calculations.
Indole-Derived Donor-Acceptor Cyclopropanes
Israel Journal of Chemistry. 2016. Т. 56. № 6-7. С. 369-384.
Abstract: Due to a combination of a broad diversity of reactivities of donor-acceptor cyclopropanes with easy functionalization of the indole ring, as well as potent bioactivity of indole ring-containing products, indole-derived donor-acceptor cyclopropanes are among the most attractive compounds. Methods for the synthesis and reactivity of donor-acceptor cyclopropanes containing the indole ring as a donor substituent are reviewed.
Villemson E.V., Budynina E.M., Ivanova O.A., Skvortsov D.A., Trushkov I.V., Melnikov M.Y.
Concise approach to pyrrolizino[1,2-b]indoles from indole-derived donor-acceptor cyclopropanes
RSC Advances. 2016. Т. 6. № 66. С. 62014-62018.
Abstract: Developed here is a direct three-step approach to a previously unexplored pyrrolizino[1,2-b]indole system based on a sequence of three synthetic steps: (a) one-pot azide ion promoted ring opening of the indole-derived donor–acceptor cyclopropane and Krapcho dealkoxycarbonylation; (b) Vilsmeier–Haack formylation; (c) tandem Staudinger/intramolecular aza-Wittig reaction and reductive cyclization realized in a one pot fashion.
Makarov A.S., Merkushev A.A., Uchuskin M.G., Trushkov I.V.
Oxidative Furan-to-Indole Rearrangement. Synthesis of 2-(2-Acylvinyl)indoles and Flinderole C Analogues
Organic Letters. 2016. Т. 18. № 9. С. 2192-2195.
Abstract: It was designed an oxidative rearrangement of 2- (2-aminobenzyl) furans leading to 2- (2-acylvinyl) indoles with high yields and controlled stereoselectivity. It was shown that the starting furans containing electron-donating alkoxy-substituents in the phenyl group only form (E) -isomers of 2- (2-acylvinyl) indoles.. In contrast, substrates without such substituents form are exclusively (Z) -isomers. A short diastereoselective method for converting the obtained indoles into close structural analogues of the flinderol alkaloids A-C exhibiting antimalarial properties has been developed.
Budynina E.M., Ivanov K.L., Chagarovskiy A.O., Rybakov V.B., Trushkov I.V., Melnikov M.Y.
From Umpolung to Alternation: Modified Reactivity of Donor-Acceptor Cyclopropanes Towards Nucleophiles in Reaction with Nitroalkanes.
Chemistry - A European Journal. 2016. Т. 22. № 11. С. 3692-3696.
Abstract: A conceptually new type of donor–acceptor cyclopropane reactivity towards nucleophiles has been disclosed. An essential characteristic of the process is an unusual nucleophilic attack on the C(3)-position of a cyclopropane, combined with typical small ring-opening by cleavage of the C(1)−C(2) bond between the acceptor and the donor. Based on this new reaction between cyclopropane-1,1-diesters and nitroalkanes, we developed a convenient approach to γ-nitroesters that can be efficiently transformed to the substituted pyrrolidones, structural analogues of racetame family drugs (rolipram, phenylpiracetam, etc.).
Chagarovskiy A.O., Budynina E.M., Ivanova O.A., Rybakov V.B., Trushkov I.V., Melnikov M.Y.
Simple assembly of polysubstituted pyrazoles and isoxazoles via ring closure–ring opening domino reaction of 3-acyl-4,5-dihydrofurans with hydrazines and hydroxylamine.
Organic & Biomolecular Chemistry. 2016. Т. 14. № 10. С. 2905-2915.
Abstract: A convenient general approach to 2-(pyrazol-4-yl)- and 2-(isoxazol-4-yl)ethanols based on the Brønsted acid-initiated reaction of 3-acyl-4,5-dihydrofurans with hydrazines or hydroxylamine was developed. Further transformation of the alcohol moiety in 2-(pyrazolyl)ethanols affording 2-(pyrazolyl)ethylamine as potent bioactive compounds as well as pyrazole-substituted derivatives of antitumor alkaloid crispine A was elaborated..
Ivanova O.A., Budynina E.M., Khrustalev V.N., Skvortsov D.A., Trushkov I.V., Melnikov M.Y.
A Straightforward Approach to Tetrahydroindolo[3,2-b]carbazoles and 1-Indolyltetrahydrocarbazoles through [3+3] Cyclodimerization of Indole-Derived Cyclopropanes.
Chemistry - A European Journal. 2016. Т. 22. № 4. С. 1223-1227.
Abstract: It was developed a new approach to the synthesis of physiologically active bisindoles based on triflate-catalyzed gallium (3 + 3) -cyclodimerization of donor-acceptor cyclopropanes based on indole It was shown that the chemoselectivity of this process depends on the position of the three-membered ring in the indole nucleus..
Budynina E.M., Ivanova O.A., Chagarovskiy A.O., Grishin Y.K., Trushkov I.V., Melnikov M.Y.
Formal [3+2]-Cycloaddition of Donor-Acceptor Cyclopropanes to 1,3-Dienes: Cyclopentane Assembly.
Journal of Organic Chemistry. 2015. Т. 80. № 24. С. 12212-12223.
Abstract: We report a new simple method to access highly substituted cyclopentanes via Lewis acid-initiated formal [3 + 2]-cycloaddition of donor–acceptor cyclopropanes to 1,3-dienes. This process displays exceptional chemo- and regioselectivity as well as high diastereoselectivity, allowing for the synthesis of functionalized cyclopentanes and bicyclic cyclopentane-based structures in moderate to high yields. Moreover, one-pot synthesis of biologically relevant cyclopentafuranones, based on reaction of donor–acceptor cyclopropanes with dienes, has been developed.
Pilipenko A.S., Uchuskin M.G., Trushkov I.V., Butin A.V.
A Simple route to g-carbolines and indolizino[7,6-b]indoles
Tetrahedron. 2015. Т. 71. № 46. С. 8786-8790.
Abstract: We designed and realized for the first time an approach to indolizino[7,6-b]indoles. This approach is based on the Leuckart–Wallach reaction of 2-(2-oxoalkyl)indoles with formamide followed by Bischler–Napieralski cyclization producing γ-carbolines. The alkylation of 3-alkyl-γ-carbolines with phenacyl bromides followed by the treatment of the formed pyridinium salt with base produced the target aromatic tetracyclic system.
Trushkov I.V., Uchuskin M.G., Butin A.V.
Furan’s Gambit: Electrophile-Attack-Triggered Sacrifice of Furan Rings for the Intramolecular Construction of Azaheterocycles
European Journal of Organic Chemistry. 2015. № 14. С. 2999-3016.
Abstract: This review summarizes the results of recent investigations of intramolecular furan ring-opening–azaheterocycle ring-closing reactions induced by acid or electrophilic attack on the furan ring.
Ivanov K.L., Villemson E.V., Budynina E.M., Ivanova O.A., Trushkov I.V., Melnikov M.Ya.
Ring Opening of Donor-Acceptor Cyclopropanes with the Azide Ion: A Tool for Construction of N-Heterocycles
Chemistry - A European Journal. 2015. Т. 21. № 13. С. 4975-4987.
Abstract: A general method for the discovery of donor-acceptor cyclopropanes by azide ion was developed. This highly regioselective and stereospecific process proceeds through the attack of the nucleophile on the more substituted C (2) atom of the three-membered ring, leading to a reversal of the configuration at the reacting atom (SN2 type reaction). All in all, polyfunctional azides were obtained with a yield of up to 91%. Their high synthetic value was demonstrated by the development of a multidirectional strategy of conversion into a variety of five-, six- and seven-member azaheterocycles, as well as complex polycyclic compounds, including the synthesis of natural compounds ((-) - nicotine) and known drugs (atorvastatin).
Rakhmankulov E.R., Ivanov K.L., Budynina E.M., Ivanova O.A., Chagarovskiy A.O., Skvortsov D.A., Latyshev G.V., Trushkov I.V., Melnikov M.Y.
Lewis and Bronsted Acid Induced (3+2)-Annulation of Donor-Acceptor Cyclopropanes to Alkynes: Indene Assembly
Organic Letters. 2015. Т. 17. № 4. С. 770-773.
Abstract: (3 + 2)-Annulation of donor–acceptor cyclopropanes to alkynes induced by both Lewis and Brønsted acids has been developed. The reaction provides a rapid approach to functionalized indenes displaying intense visible emission (λmax = 430 nm, Φ = 0.28–0.34).
Ivanova O.A., Budynina E.M., Skvortsov D.A., Trushkov I.V., Melnikov M.Y.
Shortcut Approach to Cyclopenta[b]indoles by [3+2]-Cyclodimerization of Indole-Derived Cyclopropanes
Synlett. 2014. T. 25. № 16. С. 2289-2292.
Abstract: A new straightforward approach to 3-indolyl-derived cyclopenta[ b]indoles by a Lewis acid triggered [3+2] cyclodimerization of 2-(3-indolyl)cyclopropane-1,1-dicarboxylic acid diesters was developed. This reaction exhibits exceptional chemo-, regio-, and diastereoselectivities, leading to the formation of an individual diastereomer with a relative configuration that corresponds to that of naturally occurring indole terpenoids..
Abaev V.T., Plieva A.T., Chalikidi P.N., Uchuskin M.G., Trushkov I.V., Butin A.V.
A Simple Route to Polysubstituted Indoles Exploiting Azide Induced Furan Ring Opening
Organic Letters. 2014. Т. 16. № 16. С. 4150-4153.
Abstract: A straightforward, efficient indole synthesis based on thermolysis of 2-(2-azidobenzyl)furans with attack of the formed nitrene moiety onto the ipso position of furan ring has been developed. The cyclization is accompanied by furan ring opening and affords indoles with a 2-acylvinyl substituent suitable for further modifications..
Chagarovsky A.O., Budynina E.M., Ivanova O.A., Villemson E.V., Rybakov V.B., Trushkov I.V., Melnikov M.Y.
Reaction of Corey ylide with α,β-Unsaturated Ketones: Tuning of Chemoselectivity toward Dihydrofuran Synthesis
Organic Letters. 2014. Т. 16. № 11. С. 2830-2833.
Abstract: A straightforward, efficient, and reliable approach to synthetically valuable 2,3-dihydrofurans via a reaction between Corey ylide and α,β-unsaturated ketones has been developed. The use of simple and widely spread starting materials as well as mild reaction conditions and scalability provide a broad scope of 2,3-dihydrofurans
Uchuskin M.G., Molodtsova N.V., Lysenko S.A., Strel’nikov V.N., Trushkov I.V., Butin A.V.
Synthesis of Indoles by Domino Reaction of 2-(Tosylamino)benzyl alcohols with Furfurylamines: Two Opposite Reactivity Modes of the α-Carbon of the Furan Ring in One Process
European Journal of Organic Chemistry. 2014. № 12. С. 2508-2515.
Abstract: An unusual domino reaction where the same furan α-carbon atom reacts initially as a nucleophile and then as an electrophile is reported. In the presence of acid, N-tosylfurfurylamines react with 2-(tosylamino)benzyl alcohols to afford 2-(2-acylvinyl)indoles. The reaction proceeds by Friedel–Crafts alkylation at the C(2) atom of furan followed by acid-catalyzed intramolecular nucleophilic attack of the ortho-amino group onto the same carbon atom. The replacement of the tosylamino leaving group by phthalimide enables generation of a different type of indole yet allows the ambiphilic nature of C(2) to be retained. Both types of indoles were obtained when N-furfurylbenzamides were employed.
Butin A.V., Trushkov I.V., Serdyuk O.V., Abaev V.T.
Fluorinated Furans and Benzofurans
В книге: Fluorine in Heterocyclic Chemistry. 2014. С. 181-231.
Abstract: Synthesis, reactions, and application of furans and benzofurans bearing a fluorine atom and a trifluoromethyl group are reviewed.
Ivanova O.A., Budynina E.M., Skvortsov D.A., Limoge M., Bakin A.V., Chagarovskiy A.O., Trushkov I.V., Melnikov M.Y.
A bioinspired route to indanes and cyclopentannulated hetarenes via (3+2)-cyclodimerization of do nor-acceptor cyclopropanes
Chemical Communications. 2013. Т. 49. № 98. С. 11482-11484.
Abstract: A novel Lewis acid-catalyzed domino (3+2)-cyclodimerization of 2-arylcyclopropane-1,1-diesters and related stepwise cross-reaction of two different cyclopropanes were developed. These processes provide efficient and highly stereoselective access to polyoxygenated indanes and cyclopentannulated heteroarene derivatives, which display significant cytotoxicity against several lines of cancer cells (IC50 of 10(-6)-10(-5) M) while being non-toxic for normal cells
Chagarovskiy A.O., Ivanova O.A., Budynina E.M., Kolychev E.L., Nechaev M.S., Trushkov I.V., Melnikov M.Y.
Reaction of Donor-Acceptor Cyclopropanes with 1,3-Diphenylisobenzofuran. Lewis Acid Effect on the Reaction Pathway
Russian Chemical Bulletin. 2013. Т. 62. № 11. С. 2407-2423.
Abstract Reaction of donor-acceptor cyclopropanes with 1,3-diphenylisobenzofuran in the presence of lanthanide triflates, as well as CuOTf, Sn(OTf)2, SnCl2, ZnCl2, GaCl3, and MgI2, proceeds as a formal [3+4]-cycloaddition leading to a newly formed seven-membered ring. This reaction was found to be typical of cyclopropane-1,1-diesters and dinitriles, as well as 1-nitrocyclo-propanecarboxylates containing aromatic, heteroaromatic, and vinylic substituents at the C(2) atom of the small ring. When Me3SiOTf, TiCl4, SnCl4, or BF3·OEt2 were used as initiators, unusual cyclic hemiacetals were formed via the conjugate 1,4-addition of a cyclopropane and a nucleophile to the diene moiety.
Fin’ko A.V., Babikov V.O., Pilipenko A.S., Abaev V.T., Trushkov I.V., Butin A.V.
Acid-catalyzed cascade rearrangement of 4-acetoxy-9-furylnaphtho[2,3-b]furans
Monatshefte für Chemie. 2013. Т. 144. № 11. С. 1711-1723.
Abstract: Acid-catalyzed recyclization of 4-acetoxy-9-furylnaphtho[2,3-b]furans efficiently produced naphtho[1,2-b:3,4-b’]difurans. On the other hand, 4-aminonaphtho[2,3-b]furans failed to undergo the analogous recyclization into benzo[g]furo[2,3-e]indoles. The difference in behavior of these two types of substrates was explained by employing density functional theory calculations..
Trushkov I.V., Nevolina T.A., Shcherbinin V.A., Sorotskaya L.N., Butin A.V.
Furan ring opening – pyrrole ring closure. A simple route to 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazin-3-ones
Tetrahedron Letters. 2013. Т. 54. № 30. С. 3974-3976.
Abstract: We report here an application of a furan ring opening-Paal–Knorr pyrrole synthesis sequence for the transformation of furfurylamines into 1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazin-3-ones.
Volkova Y.A., Budynina E.M., Kaplun A.E., Ivanova O.A., Chagarovskiy A.O., Skvortsov D.A., Rybakov V.B., Trushkov I.V., Melnikov M.Y.
Duality of Donor-Acceptor Cyclopropane Reactivity as a Three-Carbon Component in Five-Membered Ring Construction: [3+2] Annulation Versus [3+2] Cycloaddition
Chemistry - A European Journal. 2013. Т. 19. № 21. С. 6586-6590.
Abstract: The Lewis acid catalyzed reaction of (hetero)aryl-derived donor–acceptor cyclopropanes with alkenes can be selectively directed along a [3+2] annulation pathway (see scheme). This new process provides convenient and efficient access to indanes and other cyclopentannulated (hetero)arenes, among which polyoxygenated 1-arylindanes exhibit significant cytotoxicity against several cancer cell lines with an IC50 of 10−6–10−5 M.
The long-standing and continuous interest in efficient synthetic approaches to cyclopentanoids stems from their value as building blocks in organic chemistry and their ubiquitous occurrence as core scaffolds of numerous bioactive natural and synthetic compounds, including drugs.1
One of the most rational and straightforward synthetic routes to cyclopentane-based systems is the [3+2] cycloaddition of three-carbon 1,3-dipoles to C–C double or triple bonds. Therefore, the design of compounds that possess appropriate functionalities to serve as synthetic equivalents of 1,3-carbodipoles still remains a challenging problem in organic synthesis. Among the reported precursors of such dipoles (e.g. conjugated diazoalkenes, allenoates, sources of trimethylenemethanes, and oxyallyl cations), donor–acceptor cyclopropanes play an important role.2 In recent times, the usefulness of donor–acceptor cyclopropanes is defined by their reactivity in [3+n] cycloadditions to various unsaturated compounds. In particular, donor–acceptor cyclopropanes were found to react with various dipolarophiles affording five-membered carbo- and heterocycles through [3+2] cycloaddition,3, 4 as well as undergo [3+3] and [3+4] cycloadditions furnishing six- and seven-membered rings.5, 6 In all these processes, donor–acceptor cyclopropanes exhibit properties of typical umpolung reagents7 containing a nucleophilic center at the C atom with an acceptor group and electrophilic center at the C atom with a donor substituent
Uchuskin M.G., Pilipenko A.S., Serdyuk O.V., Trushkov I.V., Butin A.V.
From Biomass to Medicines. A Simple Synthesis of indolo[3,2-c]quinolines, antimalarial alkaloid isocryptolepine, and its derivatives
Organic & Biomolecular Chemistry. 2012. Т. 10. № 36. С. 7262-7265.
Abstract: ndolo[3,2-c]quinolines are pharmacologically attractive class of heterocyclic compounds. The method of their synthesis, based on transformation of furfural, which is a large-scale product of treatment of biomass including agricultural and forestry wastes, has been developed. This method was utilized for the total synthesis of antimalarialalkaloid isocryptolepine and its derivatives.
Chagarovskiy A.O., Ivanov K.L., Budynina E.M., Ivanova O.A., Trushkov I.V.
Reaction of Dimethyl (S)-2-(p-Tolyl)cyclopropane-1,1-dicarboxylate with Acetonitrile
Chemistry of Heterocyclic Compounds. 2012. Т. 48. № 5. С. 825-827.
Abstract: It was shown that the reaction of (3 + 2) -cycloaddition of optically pure donor-acceptor cyclopropane with acetonitrile in the presence of SnCl4 leads to the formation of racemic pyrroline. This shows that the reaction involves preliminary exposure of cyclopropane to the achiral 1,3-zwitter-ionic intermediate
Uchuskin M.G., Molodtsova N.V., Abaev V.T., Trushkov I.V., Butin A.V.
Furan ring opening – indole ring closure: SnCl2-induced reductive transformation of difuryl(2-nitroaryl)methanes into 2-(2-acylvinyl)indoles
Tetrahedron. 2012. Т. 68. № 22. С. 4252-4258.
Abstract: A simple and efficient method for the synthesis of 2-(2-acylvinyl)-3-(5-alkyl-2-furyl)indoles by reductive recyclization of bis(5-alkyl-2-furyl)(2-nitroaryl)methanes is reported. This transformation was carried out by heating the substrates with SnCl2·2H2O in ethanol. The intermediate nitrosoarene moiety interacted with the furan ring via electrophilic nitrogen attack onto the C(2) position of the furan ring. It was shown that the related bis(5-alkyl-2-thienyl)(2-nitroaryl)methanes under the same reaction conditions failed to undergo the analogous recyclization and were transformed into bis(5-alkyl-2-thienyl)(2-aminoaryl)methanes.
Pilipenko A.S., Mel’chin V.V., Trushkov I.V., Cheshkov D.A., Butin A.V.
Furan Ring Opening – Indole Ring Closure: Recyclization of 2-(2-aminophenyl)furans into 2-(2-oxoalkyl)indoles
Tetrahedron. 2012. Т. 68. № 2. С. 619-627.
Abstract: The acid-catalyzed rearrangement of 5-alkyl-2-[2-(sulfonylamino)phenyl]furans into 2-(2-oxoalkyl)indoles is described. When the N-sulfonyl group in the starting compounds was displaced by an N-acyl group, the corresponding indoles were not formed under the same reaction conditions due to the in situ indole deacylation and decomposition. The presence of an alkyl group at the C5 position of the furan ring is also crucial for the efficiency of the process. The discussed rearrangement provides a simple and efficient approach to 2-(2-oxoalkyl)indoles..
Mel’nikov M.Y., Budynina E.M., Ivanova O.A., Trushkov I.V.
Recent advances in ring-forming reactions of donor-acceptor cyclopropanes
Mendeleev Communications. 2011. Т. 21. № 6. С. 293-301.
Abstract Owing to the relative ease of ring-opening under a variety of conditions, donor–acceptor cyclopropanes serve as synthetic building blocks for construction of highly functionalized carbo- and heterocyclic compounds. Recent examples of the ring-forming reactions employing donor–acceptor cyclopropanes are discussed in the present focus article.
Ivanova O.A., Budynina E.M., Chagarovskiy A.O., Trushkov I.V., Melnikov M.Y.
(3+3)-Cyclodimerization of Donor-Acceptor Cyclopropanes. Three Routes to Six-Membered Rings
The Journal of Organic Chemistry. 2011. Т. 76. № 21. С. 8852-8868.
Abstract: The ability of donor–acceptor cyclopropanes to (3 + 3)-cyclodimerize is disclosed. It has been found that Lewis acid-induced transformations of 2-(hetero)arylcyclopropane-1,1-dicarboxylates containing electron-abundant aromatic substituents led to the construction of six-membered cyclic systems. Depending on the substrate properties and the Lewis acid applied, three types of products can be obtained: (1) 1,4-diarylcyclohexanes, (2) 1-aryl-1,2,3,4-tetrahydronaphthalenes, and (3) 9,10-dihydroanthracenes.
Ivanova O.A., Budynina E.M., Chagarovskiy A.O., Rakhmankulov E.R., Trushkov I.V., Semeykin A.V., Shimanovskii N.L., Melnikov M.Y.
Domino Cyclodimerization of Indole-Derived Donor-Acceptor Cyclopropanes: One-Step Construction of Pentaleno[1,6a-b]indole Skeleton
Chemistry - A European Journal. 2011. Т. 17. № 42. С. 11738-11742.
Abstract: The domino-cyclodimerization of 2- (1-alkylindol-3-yl) cyclopropane-1,1-diester is described with the formation of compounds having an unusual pentalene [1,6a-b] indole skeleton. The reaction, which takes place with the formation of two new cycles, three C-C bonds and four stereocenters, is characterized by exclusive chemo-, regio- and stereoselectivity, giving the product as a single diastereomer with a yield of 57-75%.
Butin A.V., Uchuskin M.G., Pilipenko A.S., Serdyuk O.V., Trushkov I.V.
Unusual Reactivity of β-(3-indolyl)-α,β-unsaturated ketones. 2-Acylvinyl group removal by phenylhydrazine hydrochloride
Tetrahedron Letters. 2011. Т. 52. № 41. С. 5255-5258.
Abstract: It was found that the reaction of β- (3-indolyl) -α, β-unsaturated ketones with phenylhydrazine hydrochloride leads to removal of the 2-acyl vinyl group from position 3 of the indole ring. The reaction proceeds through the formation of the expected 3- (3-indolyl) pyrazoline derivative, which is protonated at the C3 atom of the indole under the process conditions, which leads to cleavage of the heterocycle with aromatization of the pyrazole ring.
Butin A.V., Tsiunchik F.A., Kostyukova O.N., Uchuskin M.G., Trushkov I.V.
Furan Ring Opening – Pyridine Ring Closure: New Route to Quinolines under the Bischler-Napieralski Reaction Conditions
Synthesis. 2011. № 16. С. 2629-2638.
Abstract: A new approach to polysubstituted quinolines based on the electrophilic recyclization of 2- [2- (acylamino) benzyl] furans under the conditions of the Bischler-Napiralski reaction.
Chagarovskiy A.O., Ivanova O.A., Budynina E.M., Trushkov I.V., Melnikov M.Y.
(3+2)-Cyclodimerization of 2-arylcyclopropane-1,1-diesters. Lewis acid-induced umpolung of cyclopropane umpolung
Tetrahedron Letters. 2011. Т. 52. № 34. С. 4421-4425.
Abstract: The first example of (3 + 2) -cyclodimerization of donor-acceptor cyclopropanes with the formation of 1,2-diarylcyclopentanes is described
Butin A.V., Kostyukova O.N., Tsiunchik F.A., Uchuskin M.G., Serdyuk O.V., Trushkov I.V.
Synthesis of Tetracyclic System of 2,4-Di(tert-Butyl)-6,7-Dihydrofuro[2’,3’:3,4]cyclohepta[1,2-b]indole
Journal of Heterocyclic Chemistry. 2011. Т. 48. № 3. С. 684-690.
Abstract: For the first time, tetracyclic compounds, namely, furo[20 ,30 :3,4]cyclohepta[1,2-b]indoles were synthesized by recyclization of ortho-substituted aryldifurylmethanes containing tert-butyl groups at C5 positions of the furan rings. It was shown that [2-(benzoylamino)phenyl]bis(5-tert-butyl-2-furyl)methanes 12 are transformed into tetracycles 15 at room temperature under treatment with POCl3 in benzene solution containing some drops of water
Ivanova O.A., Budynina E.M., Chagarovskiy A.O., Kaplun A.E., Trushkov I.V., Melnikov M.Y.
Lewis Acid-Catalyzed [3+4] Annulation of 2-(Heteroaryl)cyclopropanes-1,1-dicarboxylates with Cyclopentadiene
Advanced Synthesis and Catalysis. 2011. Т. 353. № 7. С. 1125-1134.
Abstract: A novel Lewis acid-catalyzed [3+4] annulation of 2-(heteroaryl)cyclopropane-1,1-dicarboxylates with cyclopentadiene is reported. This reaction proceeds via an electrophilic attack of the Lewis acid-activated donor-acceptor cyclopropane onto cyclopentadiene followed by Friedel–Crafts intramolecular alkylation of the heteroarene substituent. This is the first general example of reactions of donor-acceptor cyclopropanes wherein the donor substituent serves as a nucleophile. The described annulation represents a convenient approach to bicyclo[3.2.1]octa-2,6-dienes with heteroarenes annulated to C(2)-C(3) bond. Its efficiency was demonstrated for a series of furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, and indolyl substituted cyclopropanes. Additionally, in the case of 2-(5-methyl-2-furyl)cyclopropane-1,1-diester we observed the predominant formation of product of the [3+4] annulation or the tetracyclic 5,8-methanocyclopenta[a]azulene derivative, depending on the reaction conditions.
Butin A.V., Tsiunchik F.A., Kostyukova O.N., Trushkov I.V.
Novel Route to Quinolines via Recyclization of Furans
Chemistry of Heterocyclic Compounds. 2011. Т. 46. № 12. С. 1539-1541.
Abstract: A new method for the synthesis of quinolines has been developed, based on the recyclization of 2- [2- (acylamino) benzyl] furans under the conditions of the Bischler-Napiralsky reaction.
Chagarovskiy A.O., Ivanova O.A., Rakhmankulov E.R., Budynina E.M., Trushkov I.V., Melnikov M.Y.
Lewis Acid-Catalyzed Isomerization of 2-Arylcyclopropane-1,1-dicarboxylates: A New Efficient Route to 2-Styrylmalonates
Advanced Synthesis and Catalysis. 2010. Т. 352. № 18. С. 3179-3184.
Abstract: A facile efficient approach to the 2-styrylmalonates via the Lewis acid-catalyzed isomerization of 2-arylcyclopropane-1,1-dicarboxylates has been developed. The efficiency of this method was demonstrated for a representative series of such cyclopropanes. The isomerization proceeds chemo-, regio- and stereoselectively to afford E-styrylmalonates in good yields
Butin A.V., Nevolina T.A., Shcherbinin V.A., Uchuskin M.G., Serdyuk O.V., Trushkov I.V.
Furan Ring Opening–Pyrrole Ring Closure: Simple Route to 5-Alkyl-2-(aminomethyl)pyrroles
Synthesis. 2010. № 17. С. 2969-2978.
Abstract: A simple method for the synthesis of 5-alkyl-2- (aminomethyl) pyrroles, based on hydrolytic disclosure of 5-alkyl furfurylamines, followed by the preparation of the pyrrole ring by the Paal-Knorr reaction.
Butin A.V., Nevolina T.A., Shcherbinin V.A., Trushkov I.V., Cheshkov D.A., Krapivin G.D.
Furan ring opening-pyrrole ring closure: a new synthetic route to aryl(heteroaryl)-annulated pyrrolo[1,2-a][1,4]diazepines
Organic & Biomolecular Chemistry. 2010. Т. 8. № 14. С. 3316-3327.
Abstract: A method of synthesis of pyrrolo[1,2-a][1,4]benzodiazepines is described. This method is based on the recyclization of N-(furfuryl)anthranilamides under treatment with an aq. HCl/AcOH system and allows one to form both diazepine and pyrrole rings in one step. The reaction proceeds via furan ring opening into a diketone moiety followed by consecutive interaction of the NH(2)-group with both carbonyl functions. The process is not efficient in the presence of alkyl or aryl groups on amide nitrogen due to competitive furfuryl cation elimination. But alkylation of pyrrolo[1,2-a][1,4]benzodiazepines yields efficiently the corresponding N-alkyl derivatives. Steric effects also prevent cyclization due to reversibility of diazepine ring formation under these reaction conditions. However, the corresponding pyrrolo[1,2-a][1,4]benzodiazepines can be obtained by a stepwise process, i.e., 1) furan ring opening with aq. HCl/AcOH and 2) cyclization of isolated aminodiketones under treatment with glacial acetic acid. Another efficient procedure for the synthesis of pyrrolo[1,2-a][1,4]benzodiazepines consists of acid-catalyzed furan ring opening of N-(furfuryl)-2-nitrobenzamides followed by treatment of the formed nitrodiketone with Fe/AcOH. It leads to a one pot reduction of nitro group to amine, cyclization into diazepine and pyrrole ring formation. This procedure is efficient both for substrates with steric demands and for N-alkyl- or N-aryl-N-(furfuryl)amides. The proposed approach can be also applied to the synthesis of parent pyrrolo[1,2-a][1,4]diazepines or their analogues annulated to heterocycles.
Butin A.V., Uchuskin M.G., Pilipenko A.S., Tsiunchik F.A., Cheshkov D.A., Trushkov I.V.
Furan Ring-Opening/Indole Ring-Closure: Pictet-Spengler-Like Reaction of 2-(o-Aminophenyl)furans with Aldehydes
European Journal of Organic Chemistry. 2010. № 5. С. 920-926.
Abstract: A new simple approach to 3-(2-acylvinyl)-2-(hetero)arylindoles has been developed. The method is based on the acid-catalysed interaction of 2-(2-aminophenyl)furans with(hetero)aromatic aldehydes. The reactions proceed under very mild conditions and lead to indoles containing a reactive α,β-unsaturated ketone moiety, which is suitable for further transformations, in moderate to good yields.
Chagarovskiy A.O., Budynina E.M., Ivanova O.A., Trushkov I.V.
First Synthesis of 2-Alkyl-5-aryl-3,3-bis(methoxycarbonyl)-4,5-dihydropyrroles
Chemistry of Heterocyclic Compounds. 2010. Т. 46. № 1. С. 120-122.
Abstract: It was shown that the interaction of donor-acceptor cyclopropanes containing two ester groups as acceptor substituents with nitriles leads to the formation of 2-alkyl-5-aryl-3,3-bis (methoxycarbonyl) -4,5-dihydropyrrols.
Butin A.V., Kostyukova N.O., Tsiunchik F.A., Lysenko S.A., Trushkov I.V.
First Example of a Synthesis of the Tetracyclic 2,4-Di(tert-Butyl)-6,7-dihydrofuro[2¢,3¢:3,4]cyclohepta[1,2-b]indole system
Chemistry of Heterocyclic Compounds. 2010. Т. 46. № 1. С. 117-119.
Abstract: We have recently studied the acid-catalyzed recyclization of ortho-substituted benzylfurans. In these reactions, the furan ring acts as a formal equivalent of a 1,4-diketone: one carbonyl group participates in the formation of a new heterocycle, while the other is liberated. In the case of arylbis(5-methyl-2-furyl)methanes, the recyclization may be accompanied by a secondary cyclization involving the liberated carbonyl group [1-5], which leads to fused tetracyclic heterocycles. In contrast, the secondary cyclization does not occur when a bulky tert-butyl group is present at C-5..
Veselov I.S., Trushkov I.V., Zefirov N.S., Grishina G.V.
Trans-4-Amino-3-hydroxypiperidines. Regio- and Stereoselective Synthesis
Russian Journal of Organic Chemistry. 2009. Т. 45. № 7. С. 1050-1060.
Abstract: trans-4-Amino-1-benzyl-3-hydroxypiperidines were synthesized by regio- and stereoselective amination of a series of 1-benzyl-3,4-epoxypiperidines with primary and secondary aliphatic, aromatic, and heterocyclic amines in the presence of lithium perchlorate. The regio- and stereoselectivity of the amination process is ensured by specific activation of the oxirane ring in epoxypiperidine derivatives. Lithium cation is coordinated simultaneously at the piperidine nitrogen atom and oxirane oxygen atom, which leads to greater extension of the C4-O bond as compared to C3-O, so that nucleophilic attack is directed at the C4 atom of the piperidine ring.
Trushkov I.V., Silaev M.M., Chuvylkin N.D.
Acyclic and Cyclic Forms of the Radicals HO4•, CH3O4•, and C2H5O4•: Ab initio Quantum Chemical Calculations
Russian Chemical Bulletin. 2009. Т. 58. № 3. С. 489-492.
Abstract: Acyclic and cyclic structures and total energies of radicals HO4 CH3O4 and C2H5O4· were calculated by ab initio quantum chemical methods. Depending on the computational method and basis sets used, the cyclic conformer of the HO4· radical is 4.8 to 7.3 kJ mol-1 more stable than the acyclic one. For the first two representatives of the homologous series of alkyl tetraoxyl radicals, CH3O4· and C2H5O4, MP2/6-311++G** calculations predict insignificant energy differences (1.2 kJ mol-1) between six-membered cyclic and acyclic conformers. Apparently, these radicals can exist in both forms.
Chagarovskiy A.O., Budynina E.M., Ivanova O.A., Grishin Y.K., Trushkov I.V., Verteletskii P.V.
Lewis acid-catalyzed reactions of donor-acceptor cyclopropanes with furan derivatives
Tetrahedron. 2009. Т. 65. № 27. С. 5385-5392.
Abstract: Lewis acid-catalyzed reactions of donor-acceptor cyclopropanes with furan derivatives
Lewis acid-catalyzed reactions of dialkyl 2-arylcyclopropane-1,1-dicarboxylates with 2,5-dimethylfuran were found to give products of [3+2]-cycloaddition to C(2)–C(3) bond, which contain reactive vinyl ether moiety. These adducts can be further transformed into various products depending on the Lewis acid, the nucleophilicity of aryl group in starting cyclopropane and the ratio of reagents. The vinyl ether moiety can attack the appropriate nucleophilic center in intramolecular or intermolecular mode or can undergo cycloaddition to the second equivalent of donor–acceptor cyclopropane. Alternatively, 2,5-diphenylfuran formed Friedel–Crafts products only when reacted with donor–acceptor cyclopropanes..
Ivanova O.A., Budynina E.M., Grishin Y.K., Trushkov I.V., Verteletskii P.V.
Lewis Acid-Catalyzed Reactions of Donor-Acceptor Cyclopropanes with Anthracenes
European Journal of Organic Chemistry. 2008. № 31. С. 5329-5335.
Abstract: The reactions of 2-aryl-1,1-cyclopropane diesters with anthracene derivatives were studied for the first time. Three kinds of reaction products are formed depending on the nature of the aryl group and the substituents in the anthracene. The first one is the product of [4+3] cycloaddition of cyclopropane to a diene moiety of anthracene. The second one also has a seven-membered ring and is formed by the Lewis acid catalyzed electrophilic attack of cyclopropane onto the C9 atom of anthracene followed by intramolecular attack of the formed arenonium ion on aryl group of the starting cyclopropane. Lastly, the common Friedel–Crafts products are formed
Butin A.V., Smirnov S.K., Tsiunchik F.A., Uchuskin M.G., Trushkov I.V.
Recyclization of (2-Aminophenyl)bis(5-tert-butyl-2-furyl)methanes into Indole Derivatives: Unusual Dependence on Substituent at Nitrogen Atom
Synthesis. 2008. № 18. С. 2943-2952.
Abstract: The recyclization of (2-aminophenyl)bis(5-tert-butyl-2-furyl)methanes under acidic conditions was studied. It was found that the extent of reaction of these substrates depends on the substituent at the nitrogen atom of the aniline moiety. N-Tosyl derivatives were converted into the corresponding 3-(5-tert-butyl-2-furyl)-2-(4,4-dimethyl-3-oxopentyl)-1-tosyl-1H-indoles. Indole formation was followed by furan ring opening in the case of N-unsubstituted substrates leading to 3-(5,5-dimethyl-1,4-dioxohexyl)-2-(4,4-dimethyl- 3-oxopentyl)-1H-indoles. The same products were obtained from N-acetyl derivatives. However, the behavior of the N-benzoyl analogues depends on the reaction conditions: at room temperature 1-benzoyl-3-(5-tert-butyl-2-furyl)-1H-indoles were formed, but debenzoylation and furan ring opening proceed with heating. These data and results of control experiments showed that the reaction mechanism consists of three successive steps: recyclization itself, deacylation of the resulting N-acylindole, and furan ring opening in N-unsubstituted 3-(2-furyl)indoles. The last step can be realized for N-unsubstituted indoles only, but the furan ring is stable for Nacylindoles. This was explained by transformation of N-unsubstituted 1H-indoles under the reaction conditions into 3H-indole tautomers. These tautomers can be considered as 2,5-dialkylfurans, which have much lower stability against acids than 2-aryl-5-alkylfurans. This tautomerization is impossible for N-acylindoles. The high acidic stability of 2-(5-tert-butyl-2-furyl)indoles supports this conclusion.
Butin A.V., Dmitriev A.S., Uchuskin M.G., Abaev V.T., Trushkov I.V.
Simple and Convenient Synthesis of 4-Unsubstituted-3-(3-oxoalkyl)isocoumarins
Synthetic Communications. 2008. Т. 38. № 10. С. 1569-1578.
Abstract: A simple transformation of 2‐alkylfurans and 2‐formylbenzoic acids into 4‐unsubstituted 3‐(3‐oxoalkyl)isocoumarins is described. It is based on the synthesis of 2‐(2‐carboxybenzyl)furans followed by their acid‐catalyzed recyclization to the target isocoumarins.
Ivanova O.A., Budynina E.M., Grishin Y.K., Trushkov I.V., Verteletskii P.V.
The Donor-Acceptor Cyclopropanes as Three-Carbon Component in [4+3]-Cycloaddition. Reaction with 1,3-Diphenylisobenzofuran
Angewandte Chemie - International Edition. 2008. Т. 47. № 6. С. 1107-1110.
Abstract: Dienophiles with a difference: 2-Aryl 1,1-bis(alkoxycarbonyl) cyclopropanes undergo the title reaction under the catalysis of ytterbium triflate (Yb(OTf)3) in excellent yield (see scheme). Under mild reaction conditions, the major product is the less stable exo isomer. At higher temperatures, the endo isomer is obtained exclusively, as the exo cycloadduct decomposes through cycloreversion..
Butin A.V., Smirnov S.K., Trushkov I.V.
The effect of N-substituent on recyclization of (2-aminoaryl)bis(5-tert-butyl-2-furyl)methanes: synthesis of 3-furylindoles and triketoindoles
Tetrahedron Letters. 2008. Т. 49. № 1. С. 20-24.
Abstract: The recyclization of (2-aminophenyl)bis(5-tert-butyl-2-furyl)methane derivatives has been studied. It was shown that the acid-catalyzed recyclization of N-tosylamides leads to the formation of 2-(3-oxoalkyl)-3-(2-furyl)indoles. In contrast, under the same reaction conditions, acetamides are transformed into indoles containing three keto groups. The acid-catalyzed removal of the acetyl group from these substrates facilitated protolytic furan ring opening. The same triketones can be directly obtained from (2-aminoaryl)bis(5-tert-butyl-2-furyl)methanes..
Gavrilova G.V., Rusetskaya I.N., Gavrilov A.A., Trushkov I.V., Krut’ko D.P.
Bromination of 4-Dichloromethyl-4-methylcyclohexa-2,5-dien-1-ones
Synthetic Communications. 2007. Т. 37. № 16. С. 2729-2736.
Abstract: Bromination of 4‐dichloromethyl‐4‐methylcyclohexa‐2,5‐dien‐1‐one and 4‐dichloromethyl‐3,4‐dimethylcyclohexa‐2,5‐dien‐1‐one has been studied. The reaction conditions required for the formation of mono‐, di‐, and tribrominated products have been optimized
Butin A.V., Dmitriev A.S., Kostyukova O.N., Abaev V.T., Trushkov I.V.
Synthesis of the 4,10-Dihydro-3H-pyridazino[1,6-b]isoquinolin-10-one System by a Furan Recyclization Reaction
Synthesis. 2007. № 14. С. 2208-2214.
Abstract: The novel 4,10-dihydro-3H-pyridazino[1,6-b]isoquinolin-10-one heterocyclic system was synthesized by acid-catalyzed recyclization of 2-(difurylmethyl)benzohydrazides as well as by recyclization of (2-carboxyaryl)difurylmethanes to isocoumarins followed by the reaction with hydrazine hydrate.
Goryunkov A.A., Ovchinnikova N.S., Trushkov I.V., Yurovskaya M.A.
Synthesis, Structures and Reactivity of Polyhalofullerenes
Russian Chemical Reviews. 2007. Т. 76. № 4. С. 289-312.
Abstract: Methods for the synthesis of polyfluoro(chloro, bromo) derivatives of C60 fullerene and their structures are described. The reactivity of these compounds is demonstrated considering redox reactions, nucleophilic substitution, radical addition, cycloaddition and electrophilic arylation.
Trushkov I.V., Brel V.K.
Unusual reactivity of 3-chloro-1-pentafluorosulfanylpropene in nucleophilic substitution reactions
Tetrahedron Letters. 2005. Т. 46. № 28. С. 4777-4779.
Abstract: Treatment of 3-chloro-1-pentafluorosulfanylprop-1-ene 1 with KCN yielded the product of prototropic rearrangement ClCHCHCH2SF5, whereas reactions with NaN3 and KSCN gave the SN2 products. Ab initio calculations at MP2/6-311++G** level are used to explain the unusual behaviour of cyanide. It was found that proton transfers from both 1 to CN− and from HCN to the anion of 1 are exothermic. In contrast, azide and thiocyanate ions are too weakly basic to deprotonate 1
Mochalov S.S., Gazzaeva R.A., Fedotov A.N., Trofimova E.V., Trushkov I.V., Zefirov N.S.
Cyclopropyl- and Allyl-Substituted Arenes in Reaction with Dinitrogen Tetroxide. Effect of Substrate Oxidation Potential on Reaction Direction
Russian Journal of Organic Chemistry. 2004. Т. 40. № 8. С. 1098-1112.
Abstract: A correlation was found between oxidation potentials of acylcyclopropanes in solution (in CH2Cl2 and CH3CN) and their HOMO energies calculated by semiempirical (AM1) and nonempirical (HF/6-31G and HF/6-31G**) methods. The correlation provides a possibility to forecast the reaction direction of the mentioned substrates and N2O4. The correlation possesses a general character. It was established for instance that arylcyclo-propanes, cyclopropylmethyl- and allylbenzenes oxidized at more positive potentials than reduction potential of NO+ and having more positive eHOMOthan 9.0 eV (AM1), 8.4 eV (HF/6-31G), and 8.3 eV (HF/6-31 G**) reacted with N2O4 following the mechanism "electron transfer radical pair recombination" affording nitroaromatic derivatives retaining the cyclopropane (or allyl) fragments. Substrates of the same type where the electron transfer to NO+ should be endothermic process and whose HOMO values are less than the above critical numbers react with N2O4 by the mechanism of electrophilic cyclopropane ring opening (with aryl and benzylcyclopropanes) or by electrophilic addition across the double C=C bond (with allylbenzenes)..
Kim S.S., Trushkov I.V., Sar S.K.
Oxidation of Alcohols with Periodic Acid Catalyzed by Fe(III)/2-Picolinic Acid
Bulletin of the Korean Chemical Society. 2002. Т. 23. № 9. С. 1331-1332.
Abstract: A new oxidizing system based on iodic acid, iron (III) salt and picolinic acid is proposed for the oxidation of primary and secondary alcohols to aldehydes and ketones.
Yurovskaya M.A., Trushkov I.V.
Cycloaddition to Buckminsterfullerene C60: Advancements and Future Prospects
Russian Chemical Bulletin. 2002. Т. 51. № 3. С. 367-443.
Abstract: Investigations on mono-[2+1]-, -[2+2]-, -[2+3]-, -[2+4]-, and polycycloaddition to fullerene are reviewed. The main reagents used in cycloaddition and the reaction mechanisms are surveyed. The possible applications of cycloadducts are considered. The review covers the investigations of the last five years as well as the most important earlier studies..
Yamashkin S.A., Trushkov I.V., Tomilin O.B., Terekhin I.I., Yurovskaya M.A.
Reactivities of 5-, 6-, and 7-(Enamino)indoles in the Synthesis of Pyrroloquinolines
Chemistry of Heterocyclic Compounds. 1998. Т. 34. № 9. С. 1050-1065.
Abstract: The concept of regioorientation is proposed for the annelation of the pyridine ring with the participation of 5-, 6-, and 7-aminoindoles. The conclusions based on the experimental data are supported by quantum-chemical calculations..
Trushkov I.V., Karchava A.V., Yurovskaya M.A.
Stereoselectivity in the Reduction of Chiral Indoles to Indolines
Chemistry of Heterocyclic Compounds. 1996. Т. 32. № 9. С. 1027-1034.
Abstract: The reduction of 2-alkylindoles containing a chiral substituent at the nitrogen atom by sodium cyanoborohydride in an acidic medium at -80°C is accompanied by the formation of indolines with S-configuration of the new chiral site at C(2). An AMI quantum chemical calculation showed that the major diastereomer has greater thermodynamic stability. However, the high diastereoselectivity of this reduction may be attributed only to the relative stability of the different conformations of the intermediate indoleninium cations leading to different diastereomers.
Trushkov I.V., Gaidarova E.L., Grishina G.V.
Quantum-Chemical Analysis of the Conformational and Diastereomeric Compostion of 1,3-Dimethyl-4-(S-phenylethylimino)piperidine
Chemistry of Heterocyclic Compounds. 1996. Т. 32. № 3. С. 308-309.
Abstract: The semiempirical quantum-chemical methods MNDO, AM1, and PM3 are used in a complete conformational analysis of 1,3-dimethyl-4- (S-phenvlethylimino)piperidine..
Trushkov I.V., Chuvylkin N.D., Koz’min A.S., Zefirov N.S.
Correlation Methods for Analyzing and Predicting Reactivities in Nucleophilic Substitution Processes
Russian Chemical Bulletin. 1995. Т. 44. № 5. С. 777-800.
Abstract: Various approaches used for analyzing and predicting reactivity in nucleophilic substitution reactions at saturated carbon atoms were systematized and compared. The similarities between these approaches, their scopes, advantages, and disadvantages were established. The trends and outlooks in the further development of qualitative and quantitative models for describing dependences of the reacfivities of substances on the physicochemical properties of substrates and nucleophiles were analyzed.
Trushkov I.V., Promyslov V.M., Chuvylkin N.D., Koz’min A.S., Zefirov N.S.
Analysis of Organic Reactions on the Framework of a Three Dimensional Reaction Diagram. 2. The Estimation of the Formation Energy of the Ion-Molecule Complexes in the Gas-Phase SN2 Reactions
New Journal of Chemistry. 1993. Т. 17. № 2. 173-180.
Abstract: The application of a newly developed three-dimensional reaction diagram for the estimation of the energy of formation of ion-molecule complexes in gas- phase S(N)2 reactions is presented. The cubic diagram and the developed mathematical model permit the explanation of the appearance of energetic minima on the reaction coordinate, predict the value of these minima, and give opportunity for the determination of the value of the barriers between them. The values of DELTAE(dest) of reactants in comparison with the state corresponding to the optimal distribution of their electron density are determined. The new parameter, tau, which is a measure of polarizability of the reacting particles is proposed.
Trushkov I.V., Chuvylkin N.D., Koz’min A.S., Zefirov N.S.
Analysis of Organic Reactions on the Framework of a Three Dimensional Reaction Diagram. 1. Cubic Diagram and Its Application to Nucleophilic Substitution Reactions
New Journal of Chemistry. 1993. Т. 17. № 2. 161-171.
Abstract: A three dimensional reaction diagram is proposed for the analysis of nucloeophilic substitution reactions. In contrast to the More O'Ferrall approach this diagram includes not only the movement of the transition state along the reaction coordinate, but also along the two perpendicular coordinates. One coordinate considers the variations on the distance between nucleophile, leaving group, and electrophilic center. The other perpendicular coordinate reflects the extent of single electron shift from one of these fragments to another. A theoretical treatment of the energy variation in the cubic diagram is developed. The main parameters which have an influence on reactivity in nucleophilic substitutions are analyzed. Comparison of the application of a cubic diagram for the analysis of reactivity with some known approaches is given.
Trushkov I.V., Zhdankin V.V., Koz'min A.S., Zefirov N.S.
Cubic Reaction Coordinate Diagram in the Nucleophilic Substitution Process
Tetrahedron Letters. 1990. Т. 31. № 22. С. 3199-3200.
Abstract: A three-dimensional diagram obtained from the More O'Ferrall plot by the addition of one more perpendicular coordinate reflecting the biradicaloid character of the transition state is proposed for analysis of SN reactions.