Laboratory of Unsaturated Heteroatomic Compounds

Head of the lab: Full Member of Russian Academy of Sciences, D. Sc., Professor Boris A. Trofimov

Tel.: (3952) 42-44-11, 51-14-31.

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History of the laboratory

The laboratory was founded in 1960 under the name laboratory of organic synthesis by the corresponding member of Russian Academy of Sciences Mikhail F. Shostakovsky and Professor Alexander S. Atavin, disciples of Academician Alexey E. Favorsky.

The research interests of the lab were focused on acetylene chemistry. Among the objects of the investigations were vinyl ethers of polyatomic alcohols, cyclic acetals, vinyl sulfides and acetylenic alcohols.

Main achievements:

· Using kinetic isotope effect of deuterium it has been shown that hydrolysis of vinyl ethers proceeds via protonation of the double bond instead of the oxygen atom;

· The first environmentally benign mercury-free technology for the production of acetic aldehyde via vinyl ethers of ethylene glycol and methyldioxolane has been realized on a pilot plant in Temirtau, Kazakhstan (60th of the XX century);

· Superbase-catalyzed addition of organic disulfides to acetylene has been discovered.

In 1970 the laboratory was reorganized to laboratory of unsaturated heteroatomic compounds. From that date till the moment the laboratory is headed by Professor, Full Member of RAS Boris A. Trofimov (photo 1):

Boris Trofimov: (1938, Tchita, Russia, East Siberia); Ph.D. equivalent, 1965, Irkutsk University; D.Sc., 1970, St. Petersburg (Leningrad) University; Head of Laboratory, Irkutsk Institute of Organic Chemistry, USSR Ac. Sc., 1970; Professor, 1974. Deputy-Director, 1990; Director, 1994, Irkutsk Institute of Organic Chemistry (now A.E. Favorsky Institute of Chemistry); Corresponding Member, Russian (former USSR) Academy of Sciences, 1990; Full Member of RAS, 2000.

Areas of research interest of B.A. Trofimov and his scientific school: organic synthesis based on acetylene and its derivatives; organic chemistry of phosphorus, sulfur, selenium and tellurium (new reactions, general methods, polymers); chemistry of heterocyclic compounds; chemistry and physical chemistry of vinyl and allenyl ethers, sulfides, polysulfides, selenides, tellurides, phosphines, phosphine oxides, azoles; addition reactions to the multiple bonds; superbase catalysts and reagents.

Major accomplishments of B.A. Trofimov and his scientific school:

· Development of the superbasicity concept and systematic application of superbase catalysts and reagents in the chemistry of acetylene, heterocyclic compounds, organic compounds of phosphorus, sulfur, selenium and tellurium, new general reactions and methods for the synthesis of organic and elementoorganic compounds (e.g., the Trofimov reaction — one-stage synthesis of pyrroles from ketoxines and acetylene; the Trofimov-Gusarova reaction — synthesis of organophosphorus compounds directly from elemental phosphorus).

· Novel commercially feasible syntheses of polyfunctional monomers, intermediates and building blocks for organic synthesis, organosulfur polymers, epoxy resins, cross-linking agents, ion-exchangers, extractants, surfactants, corrosion inhibitors, fuel additives, electroconducting, redox and photosensitive polymers, organic electrolytes, pharmaceuticals, flavors and flagrances, pesticides.

B.A. Trofimov is an author of 43 monographs and chapters in monographs, 70 reviews, over 1300 major papers (full list of publications outnumbers 2700 including more than 540 Russian and foreign patents). Promoter of 86 Ph. D. and 29 D. Sc. (habilitated) belonging to his school.

Total citation index is 6863, Hirsch index 29 (Web of Sciences).

Scientific awards of B.A. Trofimov:

Butlerov Prize of Russian Academy of Sciences, (1997);

Prize of International Academic Publishing Company “Nauka” for the best publications in “Russian Journal of Organic Chemistry” (1997, 2005), “Doklady Chemistry” (1998), “Russian Journal of General Chemistry” (2007);

Medal and Diploma of Mendeleev Reader (St. Petersburg), (2003);

“A.N. Kost” Medal awarded by International Fund “Scientific Partnership”, M.V. Lomonosov Moscow State University, D.I. Mendeleev Russian Chemical Society, (2008);

Professor Emeritus of Chemical Department of St.-Petersburg State University, (2011);

Winner of the State Prize of The Russian Federation for the great contribution to organic synthesis, development of innovation technologies, drug design and creation of novel materials (2012);

A.N. Nesmeyanov Prize of Russian Ac. Sc., for the work “Novel general method of the P-C bond formation using elemental phosphorus and superbase systems: chlorine-free one-pot method for the synthesis of organophosphorus compounds (2012);

Honorary citizen of Irkutsk region (2012).

Staff

67 employees including 16 Dr.Sc. (habilitated) and professors and 38 Ph.D.

Areas of research

The development of new atom-economic reactions of acetylene and its derivatives, fundamental heterocycles, elemental phosphorus, organophosphorus and organophosphorochalcogenic compounds involving activated anions, zwitterions, carbenes and radicals to design drugs and innovation materials (including nanocomposites) for advanced technologies:

· Novel atom-economic addition reactions of СН-acids (mainly, ketones) to acetylenes and their closest derivatives (propargylic and allenic chalcogenides) in superbase media are developed. Efficient and environmentally benign methods for the preparation of unsaturated and/or functionalized carbonyl compounds of aliphatic and aromatic series are elaborated on the basis of these reactions. Methods for identification, isolation and application of key intermediates of these reactions, alkali metal dienolates, are worked out. Novel one-pot methods for the synthesis of essential functionalized heterocycles, pyrroles, isoxazoles, pyrazoles, imidazoles, are designed. Mechanisms of the reactions found are studied both experimentally and theoretically.

· New highly efficient versions of cross-coupling of electron-deficient haloalkynes with electron-rich heterocycles in the presence of nontransition metal oxides without solvents are developed. An expeditious palladium-free alternative of the Sonogashira reaction, allowing combining the acetylene fragment with heterocyclic systems, which earlier did not tolerate this reaction, is elaborated and introduced into fine organic synthesis.

· A new strategy for the synthesis of 3(H)-pyrroles (highly reactive isomers of pyrroles due to the absence of aromatic conjugation), hitherto hardly accessible but potentially promising compounds, is developed. Fundamentally new approaches to the synthesis of scaffold structures comprising the pyrrole and pyridine rings are designed. New expedient versions of the pyrrole synthesis from ketones using synthetic equivalents of acetylene (vinylhalides, haloethanes instead of free acetylene) are elaborated. Novel modifications of the superbase catalytic media, including heterogeneous and nanostructured, are created. The chemistry of functionalized pyrroles, e.g. synthesis of dipyrrolyltriazole and dipyrrolyltetrazine ensembles, condensation products of pyrrolylcarbonitriles with hydrazine, is progressing.

· A new general strategy for functionalization of aromatic heterocycles involving zwitterions, carbenes, and vinyl carbanions, adducts of electron-deficient acetylenes with main sites of reagents, is developed.

· New direct reactions of elemental phosphorus with acetylenes, alkenes and arenes, aryl-and hetarylhalogenides in the superbase systems are elaborated and areas of application of these reactions expand. One-pot environmentally benign chlorine-free (phosphorus halogenides-free) methods for the synthesis of earlier hardly accessible organic phosphines, phosphine oxides and organophosphorus acids are worked out. These products are ligands for metal complex catalysts of the new generation, valuable solvents for stabilization of nanosystems, components of advanced nonflammable materials and nonflammable electrolytes for lithium batteries.

· New multicomponent reactions between primary or secondary phosphines, elemental chalcogens and organic (n- and π-) and inorganic bases are developed. New strategy for one-pot atom-economic synthesis of chalcogene phosphinic and chalcogene phosphonic acid derivatives, highly effective precursors for the design of semiconducting, optical and magneto-optical nanomaterials, pesticides of new generation and highly selective extracting agents for fractionation of rare, precious and radioactive metals is elaborated.

· A methodology for the synthesis of directly functionalized biopolymers and their hybrid nanobiocomposites from vegetable feedstock is developed. Novel pharmacologically active substances and innovative materials for critical technologies are designed.

Principal results

  • One-pot stereospecific assembly of novel heterocyclic systems from ketones and acetylene (Scheme 1)

Self-organization of acetylene and ketone molecules in the presence of the superbases leading to stereospecific cascade assembly of new complex heterocyclic systems, analogs of known insect pheromones, has been discovered. The reaction allows diverse aromatic and heterocyclic substituents to be introduced into the pheromone skeleton thus offering fundamentally new possibilities for organic synthesis on the basis of simple and available starting materials. The self-organization discovered originates a new concept of directed synthesis of biologically active agents and precursors of materials for advanced technologies.

Scheme 1

Trofimov B.A., Schmidt E.Yu., Ushakov I.A., Mikhaleva A.I., Zorina N.V., Protsuk N.I., Senotrusova E.Yu., Skital’tseva E.V., Kazheva O.N., Alexandrov G.G., Dyachenko O.A. One-pot assemble of 7-methylene-6,8-dioxa-bicyclo[3.2.1]octanes, congeners of frontalin, from ketones an acetylene // Eur. J. Org. Chem. — 2009. — P. 5142-5145.

  • A general methodology of vinylation of ketones with acetylenes: new reaction of the C-C bond formation (Schemes 2, 3)

A general efficient methodology for the base-catalyzed stereoselective vinylation of ketones with acetylenes has been developed. The methodology provides a short-cut to β,γ-unsaturated ketones of E-configuration, intermediates for further chemical transformations, drug design and optoelectronic materials.

The homogeneous superbase catalytic system potassium tert-butylate / dimethylsulfoxide ensures vinylation of aliphatic, cycloaliphatic, alkylaromatic and alkylheteroaromatic ketones in more than 90% yields.

Difficult-to-access (Е)-2-styrylcycloalkanones, building blocks and drug precursors, are synthesized from cycloaliphatic ketones and arylacetylenes.

Scheme 2

· Trofimov B.A., Schmidt E.Yu., Ushakov I.A., Zorina N.V., Skitaltseva E.V., Protsuk N.I., Mikhaleva A.I. Base-Catalyzed Stereoselective Vinylation of Ketones with Arylacetylenes: A New C(sp3)-C(sp2) Bond-Forming Reaction // Chem. Eur. J. — 2010. — V. 16. — P. 8516-8521.

· Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V., Ushakov I.A., Mikhaleva A.ITransition Metal-Free Stereoselective α-Vinylation of Cyclic Ketones with Arylacetylenes in the Superbasic Catalytic Triad Potassium Hydroxide/tert-Butyl Alcohol/Dimethyl Sulfoxide // AdvSynthCatal. — 2012. — V. 354, N 9. — P. 1813-1818.

· Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V., Ushakov I.ATransition-Metal-Free Superbase-Promoted Stereoselective α-Vinylation of Ketones with Arylacetylenes: A General Strategy for Synthesis of β,γ-Unsaturated Ketones // JOrg. Chem. — 2012. — V. 77, N 16. — P. 6880-6886.

Within the framework of this methodology, an unprecedented diastereoselective one-pot assembly of hexahydroazulenones, biologically and pharmaceutically important fused bicyclic systems, from2-alkylcyclohexanonesand arylacetylenes, has been discovered.

Scheme 3

Trofimov B.A., Schmidt E.Yu., Skitaltseva E.V., Zorina N.V., Protsuk N.I., Ushakov I.A., Mikhaleva A.I., Dyachenko O.A., Kazheva O.N., Aleksandrov G.G. Unexpected diastereoselective one-pot assembly of hexahydroazulenones from 2-alkylcyclohexanones and arylacetylenes in KOH/DMSO suspension // Tetrahedron Lett. — 2011. — V. 52, N 33. — P. 4285-4287.

  • A general methodology of organocatalytic alkynylation of carbonyl compounds (Scheme 4)

A general methodology for the synthesis of secondary and tertiary propargylic alcohols of aliphatic, cycloaliphatic, aromatic and heteroaromatic series has been developed. The methodology comprises organocatalytic alkynylation of aldehydes and ketones with acetylene (under atmospheric pressure) and its monosubstituted derivatives in the presence of original catalytic composition Bu4NOH/H2O/molecular sieves/DMSO. Yields of the target products reach 90%.

Scheme 4

The methodology paves a convenient, facile and green (metal-free) avenue to a number of acetylenic alcohols thus essentially expanding the scope of their application as valuable building blocks in fine and industrial organic synthesis to produce fragrant substances, vitamins, pheromones, environmentally safe insecticides, as well as inhibitors of steel acid corrosion and nonionic multi-purpose surfactants.

  • One-pot synthesis of pyrroles from ketones, hydroxyl amine and dichloroethane (Scheme 5)

A new general method for the synthesis of pyrroles from ketones and hydroxylamine in the KOH/DMSO system in the presence of dichloroethane as acetylene equivalent has been elaborated. Conversion of the ketone reaches50-95%,unreacted ketone is recovered as oxime upon treatment of the reaction mixture with aqueous alkali solution.

Scheme 5

The method allows to circumvent the existing restrictions related to application of acetylene in laboratory and industry, thereby principally expanding the possibilities of synthesis of pyrroles, important building blocks and precursors of drugs and materials for advanced.

  • New stereoselective transformation of imidazoles, essential heterocyclic systems, under the action of acetylenes (Scheme 6)

Unprecedented stereoselective opening of the imidazole cycle under the action of functional acetylenes in the presence of water to afford (Z,Z)-1,4-diaza-2,5-dienes bearing pharmacophore functional groups has been revealed. The compounds synthesized are novel potent drug precursors and building blocks for multi-purpose fine organic synthesis. The new reaction is entirely atom-economic and does not require catalysts. The results obtained expand fundamental facets of imidazole and acetylene chemistry, since for the first time aromatic imidazole ring is opened under unusually mild conditions (45-60оС) with high efficiency (up to 80% yield) and 100% stereoselectivity at both olefinic centers. The reaction is proved to proceed via zwitterionic intermediates, adducts of imidazole with acetylenes.

Scheme 6

Trofimov B.A., Andriyankova L.V., Nikitina L.P., Belyaeva K.V., Mal’kina A.G., Sobenina L.N., Afonin A.V., Ushakov I.A. Stereoselective Tandem Ring-Opening of Imidazoles with Electron-Deficient Acetylenes and Water: Synthesis of Functionalized (Z,Z)-1,4-Diaza-2,5-dienes // Org. Lett. — 2013. — V. 15, N 9. — P. 2322-2324.

  • Stereoselective synthesis of functional vinylphosphine oxides (Scheme 7)

It has been shown for the first time that vinyl carbanions of zwitterionic type, formed upon the attack of tripyridylphosphine at electron-deficient acetylenes, trigger a new stereoselective synthesis of hitherto unknown functionalized vinyldipyridylphosphine oxides. The reaction proceeds in water without catalyst upon slight heating with cleavage of theC-Pbond and abstraction of the pyridine molecule. Isomerically pure vinyldipyridylphosphine oxides represent promising ligands for metal complex catalysts, drug precursors and semi-products for organic synthesis.

Scheme 7

Arbuzova S.N., Gusarova N.K., Glotova T.E., Ushakov I.A., Verkhoturova S.I., Korocheva A.O., Trofimov B.A. Reaction of Tris(2-pyridyl)phosphine with Electron-deficient Alkynes in Water: Stereoselective Synthesis of Functionalized Pyridylvinylphosphine Oxides // Eur. J. Org. — Chem. DOI: 10.1002/ejoc.201301453

· Unexpected direction of the reaction of cyanoacetylenic alcohols with adenosine: a route to pharmacophore molecules (Scheme 8)

The tandem reaction of cyanoacetylenic alcohols with adenosine is found to proceed under mild conditions (50 mol% of K2CO3, 20-25оС,4-30 h, DMFA) in an unexpected direction: not nitrogen atoms (formally the most basic and nucleophilic), but two vicinal hydroxyl ribose groups react with the triple bond, and the regioselective tandem reaction completes with the formation of 1,3-dioxolane cycle.

Scheme 8

The reaction studied complements the fundamental chemistry of acetylene and nucleosides and offers a straightforward synthetic approach to novel functionalized nucleosides, promising building blocks for drug design.

Trofimov B.A., Nosyreva V.V., Shemyakina O.A., Mal’kina A.G., Albanov A.I. Chemo- and regioselective modification of adenosine with tertiary cyanopropargylic alcohols // Tetrahedron Lett. — 2012. — V. 53. — P. 5769-5772.

  • Synthesis of new class of highly efficient fluorophores (Scheme 9)

A general methodology for the synthesis of new class of highly efficient boradiazaindacene (BODIPY) fluorophores (in up to 90% yield) has been developed. The synthetic protocol comprises the reduction of available trofluoroacetylpyrroles, condensation of the alcohols formed with pyrroles, oxidation of dipyrrolylmethanes and complex formation of the products with boron trifluoride.

Fluorescence quantum yield exit of (Φf) of novel fluorophores is close to theoretical (1) with strong shift to long infrared region (~ 700 nm).

New fluorophores may find application in the design of supersensitive nanosensors, in optoelectronics and biological researches.

Scheme 9

Sobenina L.N., Vasil’tsov A.M., Petrova O.V., Petrushenko K.B., Ushakov I.A., Clavier G., Meallet-Renault R., Mikhaleva A.I., Trofimov B.A. A General Route to Symmetric and Asymmetric meso-CF3-3(5)-Aryl(Hetaryl)- and 3,5-Diaryl(Dihetaryl)-BODIPY Dyes // Org. Lett. — 2011. — V. 13, № 10. — P. 2524-2527.

  • Direct synthesis of tris(2-pyridyl)phosphine from elemental phosphorus and bromopyridine (Scheme 10)

A direct reaction of element phosphorus with2-bromomopyridinehas been accomplished for the first time. The reaction affords tris(2-pyridyl)phosphine, in-demand (but still hardly accessible) ligand for the design of metal complex catalysts, unique supramolecule coordination compounds for high technologies and pharmaceuticals. The reaction proceeds in multiphase superbase catalytic system KOH-DMSO and represents the first example of nucleophilic aromatic substitution with participation of the supernucleophilic nano-sized clusters formed upon disassembling of at “dismantling” of element phosphorus macromolecules under the action of activated hydroxide-ions.

The results obtained fundamentally to chemistry of phosphorus, heteroaromatic compounds and metal complexes, as well as to the theory of nucleophilic aromatic substitution.

Scheme 10

Trofimov B.A., Artem’ev A.V., Malysheva S.F., Gusarova N.K., Belogorlova N.A., Korocheva A.O., Gatilov Yu.V., Mamatyuk V.I. Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from 2-bromopyridine and elemental phosphorus // Tetrahedron Lett. — 2012. — V. 53, N 19. — P. 2424–2427.

  • Two-stage synthesis of diselenophosphinates from elemental phosphorus, selenium and alkenes (Scheme 11)

A straightforward synthesis of diselenophosphinic acid ethers directly from elemental phosphorus, selenium and alkenes in two preparative stages has been implemented. The first stage involves chlorine-free environmentally safe direct phosphorylation of alkenes by elemental phosphorus (through intermediate formation of phosphine-hydrogen mixture) in a superbase system (KOH/DMSO, 55-75оС) to deliver secondary phosphines.

The second stage comprises a new three-component, atom-economic, regioselective reaction between secondary phosphines, elemental selenium and alkenes (aryl- and hetarylalkenes, vinyl ethers, vinyl sulfides, vinyl selenides). The reaction proceeds at 85-100оС for1.5-3 h without catalyst to furnish hitherto unknown class of organophosphoselenium compounds(81-99% yield), diselenophosphinic acid ethers containing chiral carbon at the selenium atom.

Scheme 11

Trofimov B.A., Gusarova N.K. Elemental phosphorus in strongly basic media as phosphorylating reagent: a dawn of halogen-free ‘green’ organophosphorus chemistry // Mendeleev Commun. — 2009. — № 19. — P. 295–302.

Close congeners of the diselenophosphinates synthesized are employed for the preparation of semi-conducting nanomaterials, nano-structured selenium and represent polymerization regulators (“RAFT agents”) and biologically active compounds.

Gusarova N.K., Artem’ev A.V., Malysheva S.F., Tarasova O.A., Trofimov B.A. A three-component reaction between alkenes, secondary phosphanes, and elemental selenium: a novel, efficient, atom-economic synthesis of diselenophosphinic esters // Tetrahedron Lett. — 2011. — V. 52. — P 6985-6987.

  • Antimicrobial nanobiocomposite “Trojan Horse”: food capture of silver nanoparticles by microbes with the subsequent affection with free radicals and electric field of nanoparticles (Scheme 12)

An approach to the direct synthesis of new highly efficient antimicrobial agents has been elaborated. The approach is based on the idea that silver nanoparticles are encapsulated in the polysaccharide macromolecules, which represent natural food for microbes.

In the course of continuous search for food, a microbe captures the nanocomposite followed by food utilization of the polysaccharide. As a consequence, silver nanoparticle are very effectively transported and irreversibly liberated on a microbial cell. Then follows an impetuous suppression and death of the microbial cell due to direct contact with the free radicals, which source is silver nanoparticles. Besides, the most important affecting factor of silver nanoparticles is their plasmon electric field, which already remotely breaks the physiological transmembrane potential of the microbial cell, up to electric breakdown of this cell membrane.

Scheme 12

Shurygina I.A., Sukhov B.G., Fadeeva T.V., Umanets V.A., Shurygin M.G., Ganenko T.V., Kostyro Ya.A., Grigoriev E.G., Trofimov B.A. Bactericidal action of Ag(0)-antithrombotic sulfated arabinogalactan nanocomposite: сoevolution of initial nanocomposite and living microbial cell to a novel non-living nanocomposite // Nanomedicine: Nanotechnology, Biology and Medicine. — 2011. — V 7, N 6. — P. 827–833.

Awards

  • A.M. Butlerov Prize of the Russian Academy of Sciences was awarded to B. A. Trofimov and A.G. Mal’kina) for a series of works “Chemistry of a,b-acetylenic g-hydroxyacids” (1997).
  • Prize of International Academic Publishing Company “Nauka” was awarded to B.A. Trofimov, A.G. Mal’kina, A.I. Albanov, L.V. Andriyankova, Du Li, N. L. Owen, V.V. Nosyreva, and E.I. Kositsina for a series of papers entitled “Cyanoacetylene and his derivatives” published in “Russian Journal of Organic Chemistry” (1997).
  • Prize of International Academic Publishing Company “Nauka” was awarded to N.A. Nedolya, B.A. Trofimov, L. Brandsma, H.D. Verkruijsse, A.C.H.T.M. van der Kerk, O.A. Tarasova, LV. KlybaL.M. Sinegovskaya, F. Takherirasstgar, R.-J. de Lang for a series of papers entitled “Highly saturated heteroatomic carbanions as building blocks for the direct selective assembly of heterocyclic systems (pyrrole, thiophene, pyridine, quinoline, imidazole, etc.) bearing biologically important functional groups”, published “Doklady Chemistry” (1998).
  • M.A. Lavrentyev Prize for young scientists was awarded to Ph.D. S.N. Arbuzova for the research related to “Direct reactions of acetylene, its substituents, derivative as well as others electrophiles with elemental phosphorus and PH-acids in the presence of the superbase and metal complex catalysts: design of new polydentate optically active ligands, molecular optical switches, photoreceptors and luminophores” (2002).
  • Medal and Diploma of Mendeleev Reader were awarded to the academician B.A. Trofimov (St. Petersburg, 2003).
  • Grant of the President of the Russian Federation (No. MK-1663.2003.03) to support researches of young Ph.D. in the field of “Chemistry, new materials and chemical technologies” was awarded to A.P. Demenev (2003).

· Grant of the President of the Russian Federation (№ MK-3775.2004.3) to support researches of young Ph.D. in the field of “Chemistry, new materials and chemical technologies” was awarded to S.N. Arbuzova (2004).

  • Prize of International Academic Publishing Company “Nauka” was awarded to B.A. Trofimov, A.G. Mal’kina, L.A. Oparina, and L.N. Parshina for a series of papers entitled “Unknown peculiarities of the reactions of acetylenic compounds with nucleophilic reagents”, published in “Russian Journal of Organic Chemistry” (2005).
  • The diploma in the field of natural and humanitarian sciences (The program “Best PhD Students of RAS”) was awarded to V.A. Kuimov (2006).
  • M.A. Lavrentyev Prize for young scientists was awarded to N.V. Zorina for the research related to “Synthesis of pyrroles coupled with condensed aromatic and heteroaromatic or metalocene systems” (2006).
  • Grant of the President of the Russian Federation to support researches of young Dr.Sc. in the field of “Chemistry, new materials and chemical technologies” was awarded to E.Yu. Schmidt (2006-2007).
  • Grant of the President of the Russian Federation to support researches of young Ph.D. in the field of “Chemistry, new materials and chemical technologies” was awarded to V.A. Kuimov (2006-2007).
  • Prize of International Academic Publishing Company “Nauka” was awarded to B.A. Trofimov, N.K. Gusarova, S.F. Malysheva, B.G. Sukhov, V.A. Kuimov, Yu.V. Smetannikov, N.P. Tarasova for a series of papers entitled “Reactions of red phosphorus and its nanocomposites in the presence of the strong bases and electrophiles, including microwave-assisted reactions”, published in “Russian Journal of General Chemistry” (2007).
  • The medal “In memory of professor A.N. Kost” on behalf of the International charity foundation “Scientific Partnership”, Lomonosov Moscow State University and D. I. Mendeleyev Russian chemical society was awarded to Academician B.A. Trofimov (2008).
  • The diploma in the field of natural and humanitarian sciences (The program “Best PhD Students of RAS”) was awarded to M.Yu. Dvorko (2008).
  • V.A. Koptyug Prize for young scientists was awarded to Ph.D. V.A. Kuimov for development of new convenient and environmentally benign synthesis of important organophosphorus compounds from red phosphorus nanocomposites, electrophiles and strong bases (2008).
  • The Medal and Prize of the Russian Academy of Sciences for young scientists was awarded to Ph.D. O.A. Shemyakina for a series of works related to “Reactions of nitrogen-containing nucleophilic reagents with acetylenic hydroxynitriles” (2009).
  • Grant of the President of the Russian Federation (No. MK-629.2010.3) to support researches of young Ph.D. in the field of “Chemistry, new materials and chemical technologies” was awarded to V.A. Kuimov (2010).
  • Academician B.A. Trofimov was elected Professor Emeritus of Chemical Department of St.-Petersburg State University (2011);
  • Academician N.N. Vorozhtsov Prize for young scientists was awarded to Ph.D. N.V. Zorina for a series of publications entitled “Tandem assemblies of heterocyclic systems with participation of acetylenes” (2011).
  • The State Prize of the Russian Federation in the field of science and technologies was awarded to academician B.A. Trofimov for the great contribution to organic synthesis, development of innovation technologies, drug design and creation of novel materials (2012).
  • A.N. Nesmeyanov Prize was awarded to academician B.A. Trofimov, Professor N.K. Gusarova, and D.Sc. S.F. Malysheva for outstanding works in the field of chemistry the elementootganic compounds (2012).
  • Academician B.A. Trofimov was awarded Honorary citizen of Irkutsk region (2012).

Promotions in 2011-2013

D.Sc. thesis promotions

  • Ivanov A.V. “New aspects of pyrrole chemistry” (2011);
  • Shemyakina O.A. “Tandem reactions of cyanoacetylenic alcohols with nitrogen-containing nucleophiles: design of new polyfunctional heterocyclic systems” (2012);
  • Artem’ev A.V. “New multicomponent reactions in chlorine-free synthesis of phosphorus- and chalcogenoorganophosphorus acids and their derivatives” (2013).

Ph.D. thesis promotions

  • Borisova A.P. “Tandem reactions of alpha-cyanoacetylenic alcohols with amino acids” (2011);
  • Volostnykh O.G. “Structural reorganization of azatriene systems into azepines under the action of potassium tert-butoxide” (2011);
  • Mikhailenko V.L. “New syntheses of organophosphorus compounds on the basis of red phosphorus” (2011);
  • Lesnichaya M.V. “Synthesis and properties of Ag(0)- and Au(0)-containing nanocomposites on the basis of galactomannan and carrageenan” (2011);
  • Ivanova E.V. " Stereoselective nucleophilic addition of ketones to arylacetylenes (2012);
  • Bidusenko I.A. “Reactions of tertiary propargylic alcohols in the superbase media: cyclodimerization, acetalyzation, vinylation” (2013);
  • Tomilin D.N. “Functionalized 2-ethynyl-4,5,6,7-tetrahydroindoles: synthesis and reactions of acetylene substituents” (2013);
  • Kolyvanov N.A. “Reactions of additions of secondary phosphines and their chalcogene derivatives to vinyl ethers” (2013).

Grants and contracts during last three years

I. Grants of Russian Foundation of Basic Research

  • RFBR_11-03-00270 “E-stereoselective C-vinylation of ketones with monosubstituted acetylenes: new reaction of C(sp3)—C(sp2)-bond forming” (Head — Academician B.A. Trofimov)
  • RFBR_11-03-00286 “Simultaneous formation of several P-C bonds in one molecule on the basis of the reactions of PH-addends with heteroatomic di-, tri- and tetraolefins: a new methodology for the synthesis of branched functionalized polyphosphines and polyphosphine chalcogenides” (Head — Professor N.K. Gusarova)
  • RFBR_11-03-00334 “Multicomponent reactions H-phosphines with elemental chalcogens and bases: a new strategy for the synthesis of halcogenephosphinic and halcogenephosphonic acid derivatives” (Head — Dr.Sc. S.F. Malysheva)
  • RFBR_11-03-00423-a “New class of molecular switches on the basis of pendular three-centered hydrogen bonding” (Head — Professor А.V. Afonin)
  • RFBR_11-03-00203 “Tandem reaction of alpha-hydroxyalkylacetylenes with carbonic acids as a basis of new methodology for the synthesis of functionalized 3-furanones and 3-hydroxyfuranones, potential drugs and their precursors” (Head — Dr. Sc. A.G. Mal’kina)
  • RFBR_11-03-92003-NSС “Synthesis of chalogene-containing organophosphorus compounds and their metal complexes” Russia — Taiwan (Head — Academician B.A. Trofimov)
  • RFBR_12-03-90433-Ukr_а “Fundamentals of the direct formation of new hybrid nanobiocomposites on the basis of original beta-polysaccharides with a complex of tailor-made physical-chemical and biological properties, promising highly efficient nanostructured prebiotics and their sinbiotic nano-constructions for biomedicine and veterinary” (Head — Academician B.A. Trofimov)
  • RFBR_12-03-31097_mol_а “Single stage synthesis of unknown or hardly accessible sterically hindered phosphines and phosphine oxides from elemental phosphorus and new complementary electrophiles” (Head — Ph.D. A.V. Artem’ev)
  • RFBR_12-03-31618_mol_а “Zwitterionic adducts of quinolines with acylacetylenes as intermediates in the synthesis of new functionalized quinoline systems” (Head — Ph.D. K.V. Belyaeva)
  • RFBR_12-03-31631_mol_а “Oxidative cross-coupling of secondary phosphine chalcogenides with amines, alcohols and thiols: new convenient approach to the synthesis of functional derivatives of phosphinehalcogenic acids” (Head — Ph.D. P.A. Volkov)
  • RFBR_12-03-31075_mol_а “A study of regularities and synthetic potential of base-catalyzed stereoselective one-pot assembly of 7-methylene-6,8-dioxabicyclo[3.2.1]octanes from ketones and acetylene” (Head — Ph.D. N.V. Zorina)"
  • RFBR_13-03-91150-NSFC-a “New functionalized pyrrole and indole ensembles as ligands and components of metal complexes and supramolecules, promising hi-tech materials for optoelectronics and photophysics” (Head — Academician B.A. Trofimov)
  • RFBR_13-03-07013. Publishing the monograph “Chemistry of acetylene: new chapters” (Head — Professor N.К. Gusarova)

II. Grant of the President of Russian Federation to support leading scientific schools: NSh-3230.2010.3 and NSh-1550-2012.3 (Head — Academician B.A. Trofimov)

III. EU Seventh Framework Program. European Community Grant (PolyZion) “Fast Rechargeable Zinc-Polymer Battery based on Ionic Liquids”: C-Tech Innovation Limited (UK), University of Leicester (UK), Fundacion CIDETEC (Spain), Celaya Emparanza y Galdos SA (Spain), Faculdade de Ciências da Universidade do Porto (Portugal), KEMA Nederland BV (Netherlands), Hydro-Québec (Canada), Rescoll (France) (2009-2012)

IV. Grants of Siberian Branch of the Russian Academy of Sciences

  • The interdisciplinary integration project SB RAS No. 134 “Implementation of size effects in original nanobiocomposites with controlled set of magneto-, neutron-, gamma-, rentgeno-, photo-, radiosensitive and highly biospecific properties for new qualitative level of low- or noninvasive radiodiagnosis and treatment” (2012-2014). Coordinator: Academician B.A. Trofimov.
  • The project of the basic researches performed by SB RAS in collaboration with Ural Branch RAS, Far East Branch RAS, Siberian Branch of Russian Academy of Medicinal Sciences, Russian Agricultural Academy and Research Institute of Blood Circulation Pathology “Synthesis of functional nitroxyls oriented at the design of new magnetically active substances and materials” (2012-2014). Coordinator: corresponding member of RAS V.I. Ovcharenko. The head from IrICh side: Academician B.A. Trofimov.
  • Joint project of SB RAS, Mongolian Academy of Sciences and Ministry of Education, Culture and Science of Mongolia No. 19 “Elucidation of interrelation of “structure — physicochemical and biological properties of nanobiocomposites” (2012-2014).

Coordinator: Academician B.A. Trofimov.

V. CONTRACTS

  • Contract with the Ministry of Education and Science of the Russian Federation No. 14.740.11.0378 “New biomimetic biodegradable polymers on the basis of original bioutilized (co)monomers, oligomers, cross-linking agents and hardeners”. Head: Academician B.A. Trofimov (2011-2012).
  • Contract with Samsung (Korea) “Synthesis and development of new electrolyte additives for Li-ion batteries” Head: Academician B.A. Trofimov(2010-2014).
  • Contract with pharmaceutical company Farmasintez (Russia) “Synthesis of promising biologically active agents for studying of antitubercular, anticancer and immunomodulating activity”. Head: Academician B.A. Trofimov (2013).

Selected publications 2011-2013

Monographs

  • Trofimov B.A., Shmidt E.Yu., Zorina N.V. Dipyrroles from dioximes and acetylene. Synthesis and properties // Saarbrueken: Lambert Academic Publishing, 2011. — 90 pp. ISBN: 978-3-8465-2069-7. In Russian.
  • Trofimov B.A., Mikhaleva A.I., Shmidt E.Yu., Sobenina L.N. Chemistry of Pyrrole. New pages // Ed. G.A. Tolstikov. — Novosibirsk: Nauka, 2012. — 383 pp. In Russian.
  • Trofimov B.A., Shmidt E.Yu., Ivanova E.V. New base-catalyzed reaction of ketones with acetylenes // Saarbrueken: Lambert Academic Publishing, 2012. — 124 pp. ISBN: 978-3-8473-9931-5. In Russian.
  • Artem’ev A.V., Gusarova N.K., Malysheva S.F. Three-component reactions of secondary phosphines with selenium and bases: a new strategy for the synthesis of diselenophosphinates // Saarbrueken: Lambert Academic Publishing, 2012. — 155 pp. ISBN: 978-3-659-30562-7. In Russian.
  • Gusarova N.K., Mikhaleva A.I., Shmidt E.Yu., Mal’kina A.G. Chemistry of acetylene. New chapters // Ed. M.P. Egorov M.P. — Novosibirsk: Science, 2013. — 368 pp. ISBN: 978-5-02-019116-7. In Russian.
  • Trofimov A.B. Introduction in quantum chemistry: A Textbook — Irkutsk: Irkutsk State University, 2013. — 192 pp. ISBN 978-5-9624-0828-6. In Russian.

Reviews

· Artem’ev A.V., Gusarova N.K., Malysheva S.F., Trofimov B.A. Diselenophosphinates. Synthesis and applications // Org. Prep. Proced. Int. — 2011. — V. 43. — P.381-449.

· Trofimov B.A., Andriyankova L.V., Belyaeva K.V. New methodology of functionalization of the imidazole ring by alkynes // Chemistry of Heterocyclic Compounds. — 2012. — V. 48, N 1. — P.147-154.

· Gusarova N.K., Arbuzova S.N., Trofimov B.A. Novel General Halogen-Free Methodology for the Synthesis of Organophosphorus Compounds // Pure Appl. Chem. — 2012. — V. 84, N 3. — P.439-459.

· Trofimov B.A., Shmidt E.Yu. New reactions of acetylenes with ketones in the superbase media // Izv. Akad. Nauk Ser. Khim. — 2013, No. 11. — P.2292-2300.

· Nedolya N.A., Trofimov B.A. Reactions of [1,7]-electrocyclization in the synthesis of azepine derivatives. Khim. Heterotsikl. Soed. 2013. — No 1. P.166-190.

Main research papers

· Trofimov B.A., Schmidt E.Yu., Skitaltseva E.V., Zorina N.V., Protsuk N.I., Ushakov I.A., Mikhaleva A.I., Dyachenko O.A., Kazheva O.N., Aleksandrov G.G. Unexpected diastereoselective one-pot assembly of hexahydroazulenones from2-alkylcyclohexanonesand arylacetylenes in KOH/DMSO suspension // Tetrahedron Lett. — 2011. — V. 52 (33). — P.4285–4287.

· Shurygina I.A., Sukhov B.G., Fadeeva T.V., Umanets V.A., Shurygin M.G., Ganenko T.V., Kostyro Ya.A., Grigoriev E.G., Trofimov B.A. Bactericidal action of Ag(0)- antithrombotic sulfated arabinogalactan nanocomposite: сo-evolution of initial nanocomposite and living microbial cell to a novel non-living nanocomposite // Nanomedicine: Nanotechnology, Biology and Medicine. — 2011. — V. 7, N 6. — P.827–833.

· Sobenina L.N., Vasil’tsov A.M., Petrova O.V., Petrushenko K.B., Ushakov I.A., Clavier G., Meallet-Renault R., Mikhaleva A.I., Trofimov B. A. A General Route to Symmetric and Asymmetric meso-CF3-3(5)-Aryl(Hetaryl)- and 3,5-Diaryl(Dihetaryl)-BODIPY Dyes // Org. Lett. — 2011. — V. 13, N 10. — P.2524-2527.

· Tatarinova I.V., Markova M.V., Mikhaleva A.I., Morozova L.V., Petrova O.V., Sobenina L.N., Vakul’skaya T.I., Khutsishvilia S.S., Prozorova G.F., Petrushenko K.B., Yakimanskyb A.V., Mac J.Sh., Yangc G., Trofimov B.A. Cationic and free radical polymerization of N-vinyl-2,3-diphenylpyrrole.// Synthetic Metals. — 2012. — V. 162. — P. 662— 669.

· Dvorko M.Y., Schmidt E.Yu., Glotova T.E., Shabalin D.A., Usakov I.A., Kobychev V.B., Petrushenko K.B., Mikhaleva A.I., Trofimov B.A. Expedient One-Step Synthesis of Nitrogen Stilbene Analogues by Transition Metal-Free Hydroamination of Arylacetylenes with Pyrroles // Tetrahedron. — 2012. — V. 68. — N 7. — Р.1963–1971.

· Trofimov B.A., Artem’ev A.V., Malysheva S.F., Gusarova N.K., Belogorlova N.A., Korocheva A.O., Gatilov Yu.V., Mamatyuk V.I. Expedient one-pot organometallics-free synthesis of tris(2-pyridyl)phosphine from2-bromopyridineand elemental phosphorus // Tetrahedron Lett. — 2012. — V. 53, N 19. — P.2424–2427.

· Tatarinova I.V., Tarasova O.A., Markova M.V., Morozova L.V., Mikhaleva A.I., Trofimov B.A. Oligomerization of phenylferrocenylacetylene under the action of WCl6. //J. Organometallic Chem. — 2012. — V.706-707. — P.124-127.

· Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V., Ushakov I.A. Transition-Metal-Free Superbase-Promoted Stereoselective α-Vinylation of Ketones with Arylacetylenes: A General Strategy for Synthesis of β,γ-Unsaturated Ketones // J. Org. Chem. — 2012, — V. 77, N 16. — Р.6880-6886.

· Trofimov B.A., Vasil’tsov А.M., Ivanov A.V., Ushakov I.A., Schmidt E.Yu., Sobenina L.N., Mikhaleva A.I. Metallation of N-vinylpyrroles and -indoles with Hg(OAc)2: N-vinyl vs. pyrrole nucleophilic sites // Dalton Trans. — 2012. — V. 41, N 18. — P.5512-5516.

· Trofimov B.A., Schmidt E.Yu., Zorina N.V., Ivanova E.V., Ushakov I.A., Mikhaleva A.I. Transition Metal-Free Stereoselective α-Vinylation of Cyclic Ketones with Arylacetylenes in the Superbasic Catalytic Triad Potassium Hydroxide/tert-Butyl Alcohol/Dimethyl Sulfoxide // Adv. Synth. & Catal., 2012. — V. 354, N 9. — P.1813-1818.

· Trofimov B.A., Glotova T.E., Shabalin D.A., Dvorko M.Yu., Ushakov I.A., Schmidt E.Yu., Kuzmin A.V., Mikhaleva A.I. Superbase-Catalyzed [4+2] Cycloaddition of Acetylenes to 3,6-Di(pyrrol-2-yl)-1,2,4,5-tetrazine: A Facile Synthesis of 3,6-Di(pyrrol-2-yl)pyridazines // Adv. Synth. Catal. — 2013. — V. 355. — P.1535-1539.

· Schmidt E.Yu., Tatarinova I.V., Ivanova E.V., Zorina N.V., Ushakov I.A., Trofimov B.A. A One-Pot Approach to Δ2-Isoxazolines from Ketones and Arylacetylenes // Org. Lett. — 2013. — V. 15 — P.104-107.

· Trofimov B.A., Andriyankova L.V., Nikitina L.P., Belyaeva K.V., Mal’kina A.G., Sobenina L.N., Afonin A.V., Ushakov I.A. Stereoselective Tandem Ring-Opening of Imidazoles with Electron-Deficient Acetylenes and Water: Synthesis of Functionalized (Z,Z)-1,4-Diaza-2,5-dienes // Org. Lett. — 2013. — V. 15, N 9. — P.2322-2324.

· Trofimov B.A., Oparina L.A., Parshina L.N., Khil’ko·M.Ya., Tantsyrev A.P., Aleksandrova G.P. Vinylation of cellulose in superbase catalytic systems: towards new biodegradable polymer materials // Cellulose — 2013. — V. 20, N 3. — P.1201–1214.

· Gusarova N.K., Volkov P.A., Ivanova N.I., Gatilov Yu.V., Trofimov B.A. Oxidative cross-coupling between secondary phosphine selenides and thiols or dithiols: a facile regioselective synthesis of thioselenophosphinic S-esters and S-diesters // Tetrahedron Lett. — 2013. — V. 54. — P.3543-3545.

· Grischenko L.A., Parshina L.N., Kanitskaya L.V., Larina L.I., Novikova L.N., Trofimov B.A. Propargylation of arabinogalactan with propargyl halides-a facile route to new functionalized biopolymers // Carbohydr. Res. — 2013. — V. 376. — P.7-14.

 

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