History of the lab

The Head of the Laboratory of Organofluorine Compounds Professor Bagrat A. Shainyan.

In 1994, immediately after Boris Trofimov was elected as a new Director of the Institute, the laboratory of asymmetric reactions was founded, headed Prof. B. Shainyan, for developing research in the field of optically active compounds. Since 1996, the group of Dr. S. Kirpichenko from the laboratory of organoelement compounds joined the lab. Several years in the making the laboratory continued previous studies of nucleophilic vinylic substituion and synthesis of silathiacycloalkanes developing the work on enantioselective catalytic hydrogenation. With time, more and more attention was focused on the chemistry of triflates (derivatives of trifluoromethanesulfonic acid) due to collaboration with Angarsk Electrolysis and Chemical Complex, and in 2000 the laboratory was renamed to the Laboratory of Organofluorine Compounds.

Staff

1. Shainyan Bagrat Armenovich, Dr. Chem., Professor, the Head of the Laboratory. Scientific interests — organofluorine chemistry, mechanisms of reactions, conformational analysis, quantum chemical calculations.

2. Lazareva Nataliya Fedorovna, Dr. Chem., Leading Scientific Worker. Expert in the field of the chemistry of organosilicon amines, amides, silatranes.

3. Kirpichenko Svetlana Vasil’evna, Dr. Sci., Leading Scientific Worker. Expert in the field of synthetic and structural organosilicon chemistry, silaheterocycloalkanes.

4. Moskalik Mikhail Yur’evich, Dr. Sci., Senior Scientific Worker. Expert in the chemistry of triflates.

5. Meshcheryakov Vladimir Ivanovich, Dr. Sci., Senior Scientific Worker.

6. Suslova Elena Nikolaevna, Dr. Sci., Senior Scientific Worker.

7. Tolstikova Ljudmila Leonidovna, Dr. Sci., Senior Scientific Worker.

8. Ushakova Irina Vladimirovna, Dr. Sci., Scientific Worker.

9. Oznobikhina Larisa Petrovna, Dr. Sci., Junior Scientific Worker.

10. Chipanina Nina Nikolaevna, Dr. Sci., Leading Specialist of the Institute in the field of molecular spectroscopy.

11. Danilevich, Dr. Sci., Leading Engineer.

12. Shulunova Alla Mikhailovna, Leading Specialist.

Fields of Research

The interests of the Laboratory are focused on research in the following areas:

1. Chemistry of triflates, mainly the derivatives of trifluoromethanesulfonamide with the main accent on the synthesis of new compounds and investigation of their structure and reactivity.

2. Chemistry of organosilicon compounds. These studies are mainly concentrated on silaheterocyclohexanes — synthesis of new derivatives, investigation of the structure and conformational behavior in comparison with organic analogs, and polyfunctional nitrogen-containing organosilicon compounds — synthesis, structure, reactivity, Si←O, Si←N pentacoordination.

3. Investigation of intra- and intermolecular interactions in polyfunctional compounds using the methods of molecular spectroscopy and quantum chemistry. These studies are performed on the compounds synthesized both in our lab and in many other laboratories of the Institute.

4. IR and UV spectroscopy service for the Institute.

Principal Results

The Laboratory became one of world’s leading centers in the chemistry of triflamide.

· For the first time the two- and three component reactions of condensation of triflamide with formamide and amides and sulfonamides are realized resulting in various linear and heterocyclic derivatives.

· The earlier unknown reactions of oxidative triflamidation of various alkenes, linear and cyclic dienes are investigated and the structure of the formed linear, mono- and bicyclic bridge and fused heterocycles is established.

· First unsaturated derivatives of triflamide containing double, triple and cumulated double С=С bonds are synthesized.

· The results of our own and literature studies are summarized in the first in the world’s literature comprehensive review in Chemical Reviews (2013), covering structure, reactivity, functional derivatives, salts and ionic liquids, biological activity.

The Laboratory firmly occupies one of the leading positions in the field of synthesis and conformational analysis of silaheterocyclohexanes.

· A large series of silaheterocyclohexanes with nitrogen, oxygen and sulfur heteroatoms in various positions in the ring, and various substituents at the silicon atom is synthesized, including Si-chiral and Si-functional, со связями Si—H, Si—F, Si—Ph, Si—OR.

· Within the framework of interdisciplinary and international cooperation, using the methods of low-temperature NMR spectroscopy, gas-phase electron diffraction and high-level theoretical calculations the conformational analysis of silaheterocyclohexanes was performed and principal difference of their conformational behavior from that of their organic analogs was demonstrated.

The Laboratory is actively developing the studies of organosilicon amines and their analogs.

· The mutual influence of heteroatoms in the geminal motif N—C—Si of N-(silylmethyl)amines is shown to result in an enhancement of the reactivity of the amine and silyl groups as compared to organic amines and silanes.

· General methodologies for the synthesis of 1-organyl-2-azasilatran-3-ones, N-(silylmethyl)carbamates, carboxamides and phosphoramides were elaborated.

The publication activity of the Laboratory is stably high, both quantitatively and qualitatively. In the last 3 years (2011–2013) 70 publications were issued, including 55 papers (30 in foreign journals), 4 reviews (3 in foreign journals) and theses of 11 presentations on the International and Russian conferences.

Dissertations in the last three years

Moskalik M. Yu.

„Reactions of condensation and heterocyclization with participation of trifluoromethanesulfonamide”

Diss. kand. khim. nauk, 02.00.03 — organic chemistry, 2011.

Bel’skykh A.V.

„New aspects of the chemistry of heteroatomic derivatives of trifluoromethanesulfonic acid ”

Diss. kand. khim. nauk, 02.00.03 — organic chemistry, 2011.

Grants during three last years

2010–2012 RFBR 10-03-00110_а (Heterocyclic and unsaturated aliphatic derivatives of triflamide: synthesis, structure, reactivity) (Head — Professor B.A. Shainyan)

2011–2013 RFBR-DFG 11-03-91334_а: Synthesis, structural and conformational analysis of new mono- and bicyclic heterocycles containing heteroatoms N, O, S, Si (Head — Professor B.A. Shainyan)

2012–2013 RFBR 12-03-31295_mol: New approach to the synthesis of trifluoromethanesulfonamide derivatives — reactions with unsaturated compounds in oxidative systems (Head — Dr.Sci. M.Yu. Moskalik)

2013–2015 RFBR 13-03-00055_а: Synthesis and transformations of the alkenyl and alkynyl trifluoromethanesulfonamide derivatives (Head — Professor B.A. Shainyan)

2014–2016 RFBR 14-03-00923_а: Experimental and theoretical study of structure and conformational properties of silaheterocyclohexanes and their derivatives (joint project with Ivanovo State University of Chemistry and Technology, Head — Professor S.A. Shlykov)

Selected publications in the last three years

1. Kirpichenko S.V., Kleinpeter E., Ushakov I.A., Shainyan B.A. Conformational Analysis of 3-Methyl-3-silathiane and 3-Fluoro-3-methyl-3-silathiane // J. Phys. Org. Chem. — 2011, v. 24. — N 4. — P. 320–326.

2. Shainyan B.A. Electron-counting rules, three-dimensional aromaticity, and the boundaries of the Periodic Table // J. Phys. Org. Chem. — 2011, v. 24. — N 8. — P. 619–620.

3. Shainyan B.A., Suslova E.N., Kleinpeter E. Conformational Analysis of N-phenyl- and N-trifyl-4,4-dimethyl-4-silathiane 1-sulfimides // J. Phys. Org. Chem. — 2011, v. 24. — N 8. — P. 698–704.

4. Lazareva N.F. N(Silylmethyl)amines, -amides, and -amino acids: biological activity and prospects in drug synthesis // Russ. Chem. Bull. Int. Ed. — 2011. v. 60. — N 4. — P. 615–632.

5. Moskalik M.Yu., Shainyan B.A., Schilde U. Reaction of Trifluoromethanesulfonamide with Alkenes and Cycloocta-1,5-diene under Oxidative Conditions. Direct Assembly of 9-Heterobicyclo[4.2.1]nonanes // Russ. J. Org. Chem. Engl. Transl. — 2011. — v. 47, N 9. — P. 1271–1277.

6. Shainyan B.A., Meshcheryakov V.I. N,N-Diformyltrifluoromethanesulfonamide // Russ. J. Org. Chem. Engl. Transl. — 2011. — v. 47, N 12. — P. 1914–1916.

7. Lazareva N.F., Shainyan B.A., Schilde U., Chipanina N.N., Oznobikhina L.P., Albanov A.I., Kleinpeter E. Synthesis, Molecular Structure, Conformational Analysis, and Chemical Properties of Silicon-Containing Derivatives of Quinolizidine // J. Org. Chem. — 2012, v. 77. — N 5. — P. 2382–2388.

8. Shainyan B.A., Kleinpeter E. Conformational Preferences of Si-Ph,H and Si-Ph,Me Silacyclohexanes and 1,3 Thiasilacyclohexanes. Additivity of Conformational Energies in 1,1-Disubstituted Heterocyclohexanes // Tetrahedron — 2012, v. 68. — N 1. — P. 114–125.

9. Shainyan B.A., Tolstikova L.L., Schilde U. Simple methods for the preparation of N-triflyl guanidines and the structure of compounds with the CF₃SO₂N=C—N fragment. // J. Fluor. Chem. — 2012, v. 135. — P. 261–264.

10. Shainyan B.A., Chipanina N.N., Oznobikhina L.P. The basicity of sulfonamides and carboxamides. Theoretical and experimental analysis and effect of fluorinated substituent // J. Phys. Org. Chem. — 2012, v. 25. — N 9. — P. 738–747.

11. Shainyan B.A., Ushakova I.V. N-Methyl-N-(2-phenylethenyl)trifluoromethanesulfonamide // Russ. J. Org. Chem. Engl. Transl. — 2012, v. 48. — N 1. — P. 141–142.

12. Shainyan B.A., Tolstikova L.L. Trifluoromethanesulfonamides and related compounds // Chem. Rev. — 2013. — V. 113, N 1. — P. 699–733.

13. Moskalik M.Yu., Shainyan B.A., Astakhova V.V., Schilde U. Oxidative addition of trifluoromethanesulfonamide to cycloalkadienes // Tetrahedron. — 2013, v. 69. — N 2. — P. 705–711.

14. Shainyan B.A., Kuzmin A.V., Moskalik M.Yu. Carbenes and nitrenes. An overview // Comput.&Theor. Chem. — 2013, v. 1006. — P. 52–61.

15. Shainyan B.A., Kirpichenko S.V., Kleinpeter E., Shlykov S.A., Osadchiy D.Yu., Chipanina, N.N., Oznobikhina L.P. 1,3-Dimethyl-3-silapiperidine: Synthesis, Molecular Structure, and Conformational Analysis by Gas-Phase Electron Diffraction, Low Temperature NMR, IR and Raman Spectroscopy, and Quantum Chemical Calculations // J. Org. Chem. — 2013. — V. 78. — N 8. — P. 3939–3947.

16. Shainyan B.A., Kleinpeter E. Silacyclohexanes and silaheterocyclohexanes: why are they so different from other heterocyclohexanes? // Tetrahedron. — 2013, v. 69. — N 29. — P. 5927–5936.

17. Shainyan B.A., Suslova E.N. 4,4-Dimethyl-3,4-dihydro-2Н-1,4-thiasiline — the first cyclic organosilicon vinyl sulfide // Mend. Commun. — 2013. — V. 23. — P. 255–256.

18. Moskalik M.Yu., Astakhova V.V., Shainyan B.A. Unusual Reaction of Trifluoromethanesulfonamide with Diallyl Sulfide // Russ. J. Org. Chem. Engl. Transl. — 2013. — v. 49. — N 5. — P. 761–762.

19. Ushakova I.V., Shainyan B.A. Bromination-dehydrobromination/debromination of N-methyl-N-(2-phenylethenyl)trifluoromethanesulfonamide // Russ. J. Org. Chem. Engl. Transl. — 2013. — v. 49. — N 6. — P. 924–926.

20. Shainyan B.A., Danilevich Yu.S. N-Allenyl-N-benzyltrifluoromethanesulfonamide // Russ. J. Org. Chem. Engl. Transl. — 2013. — v. 49. — N 8. — P. 1112–1115.

21. Shainyan B.A., Kuzmin A.V. Sulfonyl nitrenes from different sources: computational study of formation and transformations. // J. Phys. Org. Chem. — 2014, v. 27. — N 2. P. 156–162.