Scientific school of academician B.A. Trofimov

 

The scientific school of academician B.A. Trofimov originates from large classical Russian school of academician A.E. Favorsky, scientific heritage of which covers fundamental reactions and rearrangements of acetylenes and allenes, tautomeric and skeletal transformations of functional molecules, metal acetylenides, vinyl ethers, acrylic acids, terpenes, sugars, vitamins, carbanions, carboxonium cations, free radicals, carbenes.

Academician B.A. Trofimov is the leader of the Russian, just one, research center at present time, where the chemistry of acetylene is developing successfully and where the ideas and approaches formulated by academician A.E. Favorsky have been realizing.

Boris A. Trofimov was born on October 2, 1938 in Chita. He has been living in Irkutsk since 1947. In 1955 he finished secondary school with a gold medal and entered to chemical faculty of Irkutsk State University. Having graduated from the university (1961) with honors degree, Boris Trofimov started to work in Irkutsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR (now — A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, IrICh SB RAS). His creative activity relates with this Institute, where he has been working happy and successfully since 1961, from senior laboratory assistant to Doctor of sciences, professor, full academician of Russian Academy of Science, director of the Institute.

B.A. Trofimov contribution into Russian and world science can scarcely be overestimated. His researches have considerable impact on progress in chemical science and technology in our country. B.A. Trofimov formulated and developed new research principles of organic and elementoorganic synthesis on the basis of acetylene, the chemistry of which holds a central position in Organic Chemistry because of:

  • in terms of thermodynamics, acetylene is the main product of high-temperature decomposition of diverse carbon-containing substances (oil, gas, coal, technogenic wastes);
  • the majority of reactions involving triple carbon-carbon bonds are the addition or cycloaddition reactions. They are not accompanied by the formation of side-products, i.e. they are completely atom-economic and correspond to the principles of “green” chemistry;
  • reactions with participation of acetylene do not require energy consumption. On the contrary, in most cases, they are accompanied by energy release, i.e. they are energy- saving;
  • acetylenes as starting materials, owing to their multi-faceted reactivity, ensure low-cost technologies for the synthesis of Hi-Tech products with high added values, it is in accordance with a current trend that is the change over the large-scale traditional chemical industry to specialty chemistry of advanced materials.

In this line, original acetylene-based methods for the synthesis of diverse valuable products, elaborated by B.A. Trofimov and his scientific school, are energy-efficient, resource-saving and atom-economic, i.e. environmentally benign ones.

Under the supervision of B.A. Trofimov the following three main methodologies have been developed:

1. Syntheses based on application of superbase media, reagents and catalysts.

2. Syntheses involving highly reactive zwitterions and their carbene tautomers, superbase adducts of essential heterocyclic systems with activated acetylenes.

3. The use of active surfaces of metal and salt oxides (instead of noble metal complexes) for cross-coupling of pyrroles or indoles with acetylenes.

When writing the master’s thesis (1964), B.A. Trofimov has found that vinylation of polyethylene glycols with acetylene is accelerated with lengthening of the polyether chain. This fact is explained (even before discover of crown ethers) by the increase of the medium basicity during the complex formation of alkaline metal cation with oxygen atoms. These ideas were further developed in his D.Sc. thesis defended in 1970 in Leningrad (now St. Petersburg) University. Having analyzed the data on strong bases, B.A. Trofimov has formulated for the first time the concept of “superbasicity” (1977) as “mirror reflection” of the well-known superacidity phenomenon. Catalytic systems, employed by the Trofimov’s school, comprise natural environmentally benign ions such as sodium, potassium and hydroxide ions, while the reactions are activated by non-toxic dimethyl sulfoxide which is widely used in medicine for needle-free injections and as Dimexide medicine. With the help of superbase catalysts B.A. Trofimov and his disciples have discovered a series of new reactions of acetylene as well as significantly accelerated the classical Favorsky reactions: vinylation, ethynylation, acetylene-allene isomerization.

One of the main fundamental results of B.A. Trofimov’s research is the discovery of novel highly efficient one-pot synthesis of pyrroles (fundamental structural units of such essential living systems as chlorophyll, hemoglobin, and also many medicines) from ketones and acetylene (through ketoximes). This reaction is included in monographs, textbooks and manuals (e.g. Kirk-Othmer Encyclopedia of Chemical Technology, USA) and now is referred as the Trofimov reaction. Nowadays, it finds ever-increasing application in the drug precursors and materials for advanced technologies (organic semiconductors, electro- and photochromic materials, sensors and optoelectronic devices). The history of this reaction discovery is instructive. In the early seventies of the last century, Boris Trofimov asked young Ph.D. Al’bina Mikhaleva (nowadays she is D.Sc., Professor, head of large research team) to synthesize oxime vinyl ethers from acetylene in a superbase catalytic system. Dr. Mikhaleva has obtained a product, which had nothing in common with the expected one. The first intention of the researchers, as it frequently happens in such cases, was a desire to stop further experiments. However, Boris Trofimov always advises: look for unusual, unexpected, and extraordinary in any trivial things in every experiment. Never throw away an undesirable product: it may hide a discovery. Indeed, more thorough study showed that the compound synthesized by Dr. Mikhaleva belonged to the class of pyrroles. It was absolute surprise! Further investigations confirmed that a new general method for the synthesis of these valuable compounds was elaborated, thus provided the shortest and the cheapest route to their preparation.

Recently, the world’s first technology for the production of synthetic indole from cyclohexanone and acetylene has been developed on the basis of the Trofimov’s reaction. This finding was surveyed in D.Sc. thesis (2011) of B.A. Trofimov’s disciple, Andrey Ivanov, who has received a doctor’s degree in 31 years. Now the pilot plant capable of producing 200 tons of indole per year is designed. The technology allows synthesizing simultaneously tetrahydroindole (extremely expensive reactant), its vinyl derivatives and N-vinylindole, valuable semi-products and monomers which are currently not produced in the world.

Another important direction which essentially complements basic chemistry of acetylenes cross-coupling with fundamental heterocyclic compounds is developing in research group headed by Professor A.I. Mikhaleva. Such reactions are usually implemented in the presence of palladium catalysts or exotic metal complexes. A new type of cross-coupling reactions, elaborated under the supervision of B.A. Trofimov, have occurred on active surfaces of widely available metal oxides and salt (Al2O3, CaO, ZnO, K2CO3). This methodology allows one for the first time to effectively introduce functionalized acetylene substituents into the pyrrole and indole rings and thus directly synthesize novel important precursors of pharmacologically active substances. Another B.A. Trofimov’s disciple, D.Sc. Lyubov N. Sobenina, made a great deal of efforts in the development of this chemistry. It should be noted that these investigations are in keeping with two research directions which have been awarded recently by Nobel Prize, namely the reactions on active surfaces (G. Ertl, 2007) and cross-coupling reactions (R. Heck, E. Negishi, A. Suzuki, 2010).

The superbase catalysts allowed B.A. Trofimov and his disciples to develop for the first time technologically feasible methods for the synthesis of organophosphorus, -sulfur, -selenium and —tellurium compounds via direct reactions of elemental phosphorus and chalcogens with acetylenes and other industrially available electrophilic reagents (styrenes, vinylpyridines, organic halides, alkene oxides). As applied to elemental phosphorus these syntheses are referred to as the Trofimov-Gusarova reaction. As a consequence, a series of new promising monomers, precursors of hitherto unknown hi-tech polymers, ligands for metal complex catalysts, precursors of the nanostructured materials for advanced technologies, components of lithium and polymeric zinc batteries for electric vehicles, have been synthesized. Thus, new chlorine-free and environmentally friendly methods for the synthesis of organic compounds of phosphorus and chalcogens have been elaborated and now are rapidly progressing under the supervision of B.A. Trofimov. In 2012, Boris A. Trofimov and his disciples, D.Sc. Professor Nina K. Gusarova and D.Sc. Svetlana F. Malysheva were awarded A.N Nesmeyanov Prize for the work entitled “A new general method of the P-C bond formation using elemental phosphorus and superbase media: chlorine-free one-pot synthesis of organophosphorus compounds”.

B.A. Trofimov together with his disciples D.Sc. Anastasia G. Mal’kina, D.Sc. Lyudmila V. Andriyankova and D.Sc. Olesya A. Shemyakina work out a new fundamental methodology for the functionalization of essential heterocycles (pyrroles, imidazoles, pyridines, quinolines, etc.), nucleic bases and amino acids with activated acetylenes (cyanoacetylenes) via superbase zwitterionic adducts. This methodology opens extremely facile and expedient routes to the synthesis of anti-HIV medicines, vitamins and antibiotics. For this research, in 1997 B.A. Trofimov and A.G. Mal’kina were awarded one of the most prestigious prizes of the Russian Academy of Sciences, A.M. Butlerov Prize.

A while ago, academician B.A. Trofimov together with another his talented disciple, D.Sc. Elena Yu. Shmidt, has opened a new general reaction of carbon-carbon bond formation, i.e. the addition of ketones to acetylene in the presence of superbase catalysts. As a result, new cascade one-pot assemblies of complex polycyclic compounds, the structure of which is close to insect pheromones and mammal hormones, are implemented. Among such assemblies is, first of all, chemo-, regio- and stereoselective synthesis of methyleneoxabicyclooctanes from two molecules of ketones and two molecules of acetylene. A key stage of this assembly is the addition of ketones as C-nucleophiles to the triple carbon-carbon communication. Also, astoundingly surprising is chemo-, regio- and stereoselective one-pot assembly of azulenones from 2-alkylhexanones and arylacetylenes. The general fundamental feature of these cascade reactions is the combination and cooperative interaction of all imaginable transformations of acetylenes with participation of anions. It is obvious that all these reactions are of paramount synthetic potential (though not unveiled yet) and in the next years they will be intensively developed.

Under the supervision of B.A. Trofimov, in a group headed by Ph.D. B.G. Sukhov, another research direction related to the design of innovation materials and drugs is developed. The group is engaged in elaboration of new general approach to the synthesis of nanosystems, nanoreagents and nanoreactors on a basis of hemicelluloses and other biopolymers. The synthesized nanobiocomposites represent metal or metal oxide nanoparticles encapsulated in the polymeric matrix. They exhibit a sinergysm of properties of the polymeric matrix (membrane-transporting, immunomodelling, athrombogenic and antiatherogenic, water solubility, biocompatibility, rotation of the polarized light) and the nanonophase material (universal antimicrobic, antianemic activity, ferro-or superparamagnetism, plasmon resonance, catalytic activity).

Many practically valuable technologies elaborated by academician B.A. Trofimov’s school have been implemented (in seventieths — ninetieths of the last century) on pilot plants and industrial scales. Among them are novel expedient methods for the synthesis of vinyl ethers of alcohols, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, ethanolamine vinyl ethers (D.Sc. L.N. Parshina, Ph.D. L.A. Oparina), pentaerythritol tetravinyl ether (D.Sc. S.F. Malysheva), acetylenic alcohols, N-vinyltetrahydroindole, N-vinylcarbazle (D.Sc., Professor A.I. Mikhaleva, D.Sc. L.N. Sobenina) as well as novel materials on their basis for various branches of economics and defense industry. Due to innovation-driven progress growth in the country these technologies can be again demanded, modified and improved.

The methodologies of organic and elementoorganic synthesis developed by academician B.A. Trofimov and his school has gained universal recognition. Under his supervision, international projects and contracts were carried out, continues to be carried out with the following foreign research teams and the industrial companies: BASF, Germany (innovative technologies involving acetylene), Samsung, Korea (elaboration of lithium-ion and solar batteries of new generation), Moltec Corp. and Sion Power Corp., the USA (development of first lithium-sulfur batteries), PPG, the USA (epoxidation and amination of lignin), D’Alembert Institute, France (development of nanocrystalline fluorescent sensors on a basis of pyrroles), CIDETEC research center, Spain (synthesis of electrochromic polymers), Institute of Chemistry, Academy of Sciences of China (design of optoelectronic devices for advanced technologies), National Dong Hwa university, Taiwan (synthesis of semiconducting materials from metal complexes of chalcogen-containing organophosphorus compounds).

Research school of any scientist is inseparable from his or her disciples. Training activity of academician B.A. Trofimov’s school is brightly exemplified by a number of researches belonging to it. Among them are D.Sc. (29) and Ph.D. (89).

Members of the school are winners of grants of the Russian foundation of basic research (among the winners of the last three years are B.A. Trofimov, Professor, D.Sc. A.V. Afonin, Professor, D.Sc. N.K. Gusarova, Professor, D.Sc. N.A. Nedolya, D.Sc. L.V. Andriyankova, D.Sc. A.G. Mal’kina, D.Sc. S.F. Malysheva, D.Sc. L.N. Sobenina, Ph.D. B.G. Sukhov as well as young Ph.D. who won the nomination “my first grant”: A.V. Artem’ev, K.V. Belyaeva, P.A. Volkov, N.V. Zorina, D.N. Tomilin), laureates of the program “Outstanding scientists. Ph.D. and D.Sc. of the Russian Academy of Sciences” (D.Sc. E.Yu. Schmidt, 2006) and “The best Ph.D. students of the Russian Academy of Sciences” (V.A. Kuimov, 2006, M.Yu. Dvorko, 2008), winner of academician V.A. Koptyug Prize (Ph.D. V.A. Kuimov, 2008), winner of academician N.N. Vorozhtsov Prize (Ph.D. N.V. Zorina, 2011). In 2009 O.A. Shemyakina was awarded The Medal of the Russian Academy of Sciences for young scientists, and in 2010 Ph.D. V.A. Kuimov won a grant of the President of the Russian Federation for young scientists.

Finally, the most important recognition of outstanding merits of academician B.A. Trofimov is a State Prize of the Russian Federation (the highest scientific award in Russia) in the field of science and technologies which he was awarded in 2011.

References

1. Trofimov B.A. Acetylene and its Derivatives in Reactions with Nucleophiles: Recent Advances and Current Trends. Current Organic Chemistry. — 2002. — V. 6. — № 13. — P. 1121-1162.

2. Trofimov B.A., Gusarova N.K. Acetylene: new possibilities of classical reactions // Usp. Khim. — 2007. — V. 76, № 6. — P. 550-570.

3. 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, N 19. — P. 295–302.

4. 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.

5. 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.

6. Trofimov B.A., Mikhaleva A.I., Schmidt E.Yu., Sobenina L.N. Chemistry of pyrrole. New pages // Ed. G.А. Tolstikov. — Novosibirsk: Nauka, 2012. — 383 p. ISBN: 978-5-02-019070-2.

7. 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.

8. 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.

9. 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.

10. 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.

11. Gusarova N.K., Mikhaleva A.I., Schmidt E.Yu., Mal’kina A.G. Acetylene chemistry. New chapters. // Ed. M.P. Egorov. — Novosibirsk: Nauka, 2013. — 368 p. ISBN: 978-5-02-019116-7.

12. 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.

13. 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.

14. 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.

 

 

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