Synthetic organic chemistry, metal catalysis, fluoroorganic chemistry, chemistry of biologically active compounds.
Main scientific achievments:
New methodology for the synthesis of cyclic a-amino acids and their phosphorus analogs based on ring closing metathesis of diolefines and enynes under ruthenium catalysis has been developed.
An efficient method for the preparation of 3-trifluoromethyl- and 3-difluoromethyl-thalidomides — analogs of drugs for treatment of painful inflammations associated with leprosy — has been elaborated.
The first stereoselective synthesis of fluorinated bicyclo[3.1.0]hexane and [4.1.0]heptane aminoesters by ruthenium catalysed tandem addition of diazoalkane/cyclopropanation of enynes containing the fragment of a-CF3-a-amino acid has been accomplished. This reaction is highly stereosective and leads to either Z- or E-configuration of the alkenyl chain, depending on the nature of the diazoalkane and reaction conditions.
New synthetic pathway to unique trifluoromethyl substituted unsaturated systems: diolefins, enynes and allenynes has been developed. The method is based on [2,3]-sigmatropic rearrangement of allyl (or propargyl) group in trifluoromethyl-containing nitrogen and sulphur ylides in situ generated from the corresponding a-CF3-a-diazocarboxylate and phosphonate under Cu-catalysis.
A number of noval heterocyclic systems structurally resembled to some natural alkaloids has been obtained via metal-catalyzed carbocyclizations of fluorinated dienes, enynes and allenynes.
Some recent publications:
1. M. Eckert, F. Monnier, G.T. Shchetnikov, I.D. Titanyuk, S.N. Osipov, S, Dérien, P.H. Dixneuf. Tandem catalytic carben addition/bicyclization of enynes. One-step synthesis of fluorinated bicyclic aminoesters by ruthenium catalysis, Org. Lett., 2005, 3741.
2. D.V. Vorob’eva, I.D. Titanyuk, I.P. Beletskaya, S.N. Osipov. Synthesis of trifluoromethyl-containing depsipeptides via OH-insertion of rhodium carbenoid into carboxylic group of N-protected a-amino acids, Mendeleev Commun., 2005, 6, 222.
3. I.D. Titanyuk, D.V. Vorob’eva, I.P. Beletskaya, S.N. Osipov, 1-Trifluoromethyl-1-diethoxyphosphoryl Carbene - New Synthon for the Preparation of CF3-Containing a-Hydroxy and a-Amino Phosphonic Acid Derivatives, Synlett, 2006, 1355.
4. H. Skarpos, D. V. Vorob’eva, S. N. Osipov, I.L. Odinets, E. Breuer, G.-V. Roeschenthaler, A simple Pathway to N-Oxalyl and N-Phosphonoformyl Derivatives of a-Tfm a-Amino Acids, Org. Biomol. Chem, 2006, 4, 3669.
5. H. Skarpos, S.N. Osipov, D.V. Vorob’eva, I.L. Odinets, E. Lork, G.-V. R.oschenthaler, Synthesis of functionalized bisphosphonates via click chemistry, Org. Biomol. Chem., 2007, 5, 2361.
6. G.T. Shchetnikov, A.S. Peregudov, S.N. Osipov, Effective pathway to the a-CF3-substituted azahistidine analogues, Synlett, 2007, 1, 136.
7. I.D. Titanyuk, I.P. Beletskaya, A.S. Peregudov, S.N. Osipov, Trifluoromethylated cyclopropanes and epoxides from CuI-mediated transformations of α-trifluoromethyl-diazophosphonate, J. Fluorine Chemistry, 2007, 128, 723.
13. D.V. Vorobyeva, N.M. Karimova, T.P. Vasilyeva, G.T. Shchetnikov, S.N. Osipov, I.L. Odinets, G.-V. Röschenthaler, Synthesis of functionalized a-CF3-a-aminophosphonates via Cu(I)-catalyzed 1,3-dipolar cycloaddition, J. Fluorine Chem., 2010, 131(3), 378-389.
14. G.T. Shchetnikov, M.A. Zotova, C. Bruneau, P.H. Dixneuf, Synthesis of α-alkynyl-β,β,β-trifluoroalanine derivatives by Sonogashira cross-coupling reaction, Eur. J. Org. Chem., 2010, 1587.
15. X. Miao, A. Blokhin, A. Pasynskii, S. Nefedov, S.N. Osipov, T. Roisnel, C. Bruneau, P.H. Dixneuf, Alkylidene-Ruthenium-Tin Catalysts for the Formation of Fatty Nitriles and Esters via Cross-Metathesis of Plant Oil Derivatives, Organometallics, 2010,29 (21), 5257.