Ilya D. Gridnev

Tohoku University, Sendai-shi, Miyagi, Japan

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Publications (133)557.29 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: A palladium-catalyzed asymmetric addition of arylboronic acids to nitrostyrene is reported. The catalytic system employing iPr-IsoQuinox as a chiral ligand in MeOH solvent under an air atmosphere provides the chiral diarylsubstituted products in high yields with good enantioselectivities. A variety of functionalized nitrostyrenes can be used, and the method tolerates some variation in arylboronic acid scope. The stereochemical outcome can be explained using a stereochemical model.
    Organic Letters 04/2015; 17(9). DOI:10.1021/acs.orglett.5b00863 · 6.32 Impact Factor
  • Ilya D. Gridnev · Tsuneo Imamoto
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    ABSTRACT: Herein, we provide an evidence showing that the long-held major-minor concept for catalytic asymmetric reactions needs to be re-addressed. The asymmetric hydrogenation of enamide 1 catalyzed by the chiral Rh(I) complex of (R,R)-BenzP* quantitatively yields the corresponding hydrogenated R-product 2 with 89.6% ee. The most abundant catalyst-substrate species in the reaction pool was found to be [Rh((R,R)-BenzP*)(Ph(MeCONH)C=CH2)]+SbF6- (5). This spe-cies is also the most reactive to hydrogen among the various Rh-complexes. Low temperature hydrogenation experi-ments showed direct transformation of 5 to 2 with over 98% ee (R). However, the oxidative addition of H2 to 5, would yield the S-product. Computation has now revealed a low energy R-enantioselective route, whereby H2 addition to 5 is followed by -bond dissociation, isomerization of non-chelating Rh species, and re-coordination of the double bond before C-H bond formation occurs.
    ACS Catalysis 04/2015; 5(5):2911-2915. DOI:10.1021/acscatal.5b00424 · 7.57 Impact Factor
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    Ilya D. Gridnev · Andrey Kh. Vorobiev
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    ABSTRACT: Recent observation of the acetal species in the course of autoamplifying Soai reaction was analysed by the formal kinetic analysis of the experimental data and DFT computations. Kinetic analysis demonstrated convincingly that the observed species cannot be a precursor of the reaction product. Hence, it is an off-loop species that is not important for the process of the chirality amplification. DFT search for a kinetically stable acetal species resulted in the location of a Zn3 cluster stabilized with three Zn-O-Zn bridges.
    Bulletin of the Chemical Society of Japan 02/2015; 88(2):333-340. DOI:10.1246/bcsj.20140341 · 2.22 Impact Factor
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    Mao Quan · Guoqiang Yang · Fang Xie · Ilya D. Gridnev · Wanbin Zhang
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    ABSTRACT: A palladium-catalyzed asymmetric arylation of cyclic N-sulfonyl ketimine esters is described. The desired products could be prepared with excellent yields (up to 99%) and enantioselectivities (up to 99% ee) under mild reaction conditions. Furthermore, a possible reaction mechanism was determined using DFT calculations.
    02/2015; 2(4). DOI:10.1039/C4QO00347K
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    ABSTRACT: The cyanosporasides A–F are a collection of monochlorinated benzenoid derivatives isolated from the marine actinomycetes Salinispora and Streptomyces sp. All derivatives feature one of two types of cyanocyclopenta[a]indene frameworks, which are regioisomeric in the position of a single chlorine atom. It is proposed that these chloro-substituted benzenoids are formed biosynthetically through the cycloaromatization of a bicyclic nine-membered enediyne precursor. Herein, we report the synthesis of such a bicyclic precursor, its spontaneous transannulation into a p-benzyne, and its differential 1,4 hydrochlorination reactivity under either organochlorine or chloride-salt conditions. Our bioinspired approach culminated in the first regiodivergent total synthesis of the aglycons A/F and B/C, as well as cyanosporasides D and E. In addition, empirical insights into the site selectivity of a natural-like p-benzyne, calculated to be a ground-state triplet diradical, to hydrogen, chlorine, and chloride sources are revealed.
    Angewandte Chemie International Edition 12/2014; 53(50). DOI:10.1002/anie.201408416 · 11.26 Impact Factor
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    [Show abstract] [Hide abstract]
    ABSTRACT: The cyanosporasides A–F are a collection of monochlorinated benzenoid derivatives isolated from the marine actinomycetes Salinispora and Streptomyces sp. All derivatives feature one of two types of cyanocyclopenta[a]indene frameworks, which are regioisomeric in the position of a single chlorine atom. It is proposed that these chloro-substituted benzenoids are formed biosynthetically through the cycloaromatization of a bicyclic nine-membered enediyne precursor. Herein, we report the synthesis of such a bicyclic precursor, its spontaneous transannulation into a p-benzyne, and its differential 1,4 hydrochlorination reactivity under either organochlorine or chloride-salt conditions. Our bioinspired approach culminated in the first regiodivergent total synthesis of the aglycons A/F and B/C, as well as cyanosporasides D and E. In addition, empirical insights into the site selectivity of a natural-like p-benzyne, calculated to be a ground-state triplet diradical, to hydrogen, chlorine, and chloride sources are revealed.
    Angewandte Chemie 12/2014; 126(50). DOI:10.1002/ange.201408416
  • [Show abstract] [Hide abstract]
    ABSTRACT: Corresponding author. Fax: +81 22 795 6581.
    Mendeleev Communications 11/2014; 24(6). DOI:10.1016/j.mencom.2014.11.008 · 1.15 Impact Factor
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    ABSTRACT: Chiral phosphoric acids have emerged as promising asymmetric Brønsted acid catalysts that harness hydrogen bonding interactions as key stereocontrolling elements. A new approach to chiral phosphoric acid catalysis through ion-pairing interactions between the anionic conjugate base of the catalyst and a cationic electrophile has recently attracted attention. However, the mechanism of stereocontrol through ion-pairing interactions is still elusive. As a probe reaction for studying the stereocontrolling element involved in such catalytic reactions, we investigated the Petasis–Ferrier-type rearrangement of a 7-membered cyclic vinyl acetal catalyzed by chiral phosphoric acids. DFT calculations suggested that non-classical C–HO hydrogen bonds between the catalyst and the substrate play an important role in determining the stereoselectivity. In addition, π–π stacking interactions were found to be a key factor for stereocontrol when using a 9-anthryl group-bearing catalyst.
    Chemical Science 07/2014; 5(9). DOI:10.1039/C4SC00611A · 9.21 Impact Factor
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    ABSTRACT: Allylic alcohols were directly used in Pd-catalyzed allylic alkylations of simple ketones under mild reaction conditions. The reaction proceeded smoothly at 20 °C by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier.
    Angewandte Chemie 06/2014; 126(26). DOI:10.1002/ange.201403410
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    ABSTRACT: Allylic alcohols were directly used in Pd-catalyzed allylic alkylations of simple ketones under mild reaction conditions. The reaction proceeded smoothly at 20 °C by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier.
    Angewandte Chemie International Edition in English 06/2014; 53(26). DOI:10.1002/anie.201403410 · 13.45 Impact Factor
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    ABSTRACT: DFT (density functional theory) computations of the chemical fixation of copper ions on the naturally functionalized surface of nanodiamond crystallites bound by (111) planes revealed exothermic formation of chelate Cu complexes with two appropriately located carboxylic groups on the (111) surface. The irreversible strict fixation of copper ions is achieved via removing acetic acid in low-pressure conditions yields the corresponding chelate complexes not bearing any other ligands except for the surface carboxylic groups. Optimization of positional isomers of the chelating complexes showed that complexation is more likely to take place near the edges (linear ribs) of the nanoparticle. Nearby functional groups like –F, –Cl, or –OH substituents on the surface strongly affect the structures and stabilities of the resulting chelate complexes. Some of the copper atoms may be incorporated into unusual Cu(III) complexes with Cu–C covalent bonds.
    Bulletin of the Chemical Society of Japan 06/2014; 87(6):693-704. DOI:10.1246/bcsj.20130345 · 2.22 Impact Factor
  • Yuanyuan Liu · Ilya D Gridnev · Wanbin Zhang
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    ABSTRACT: The mechanism of the asymmetric hydrogenation of exocyclic α,β-unsaturated carbonyl compounds with the (aS)-Ir/iPr-BiphPhox catalyst was studied by NMR experiments and DFT computational analyses. Computed optical yields of the asymmetric hydrogenation proceeding by an iridium(I)/iridium(III) mechanism involving a transition state stabilized through two intramolecular hydrogen bonds are in good accordance with the experimental ee values.
    Angewandte Chemie International Edition 02/2014; 53(7):1901-5. DOI:10.1002/anie.201309677 · 11.26 Impact Factor
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    Ilya D. Gridnev · Yuanyuan Liu · Tsuneo Imamoto
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    ABSTRACT: The mechanism of asymmetric hydrogenation of five representative β-dehydroamino acids catalyzed by rhodium complexes of (R)-(tert-butylmethylphosphino)(di-tert-butylphosphino)methane (trichickenfootphos, TCFP) and (R,R)-1,2-bis(tert-butylmethylphosphino)benzene (BenzP*) was studied through a combination of extensive NMR experiments and state-of-the-art DFT computations in order to reveal the crucial factors governing the sense and order of enantioselectivity in this industrially important reaction. The binding mode of the substrate with a Rh(I) catalyst was found to be highly dependent on the nature of the rhodium complex and the substrate. Thus, no substrate binding was detected for [Rh((R,R)-BenzP*)S2]+SbF6– (5) and (E)-3-acetylamino-2-butenoate (2a) even at 173 K. [Rh((R)-TCFP) S2]+BF4– (3) exhibited weak reversible binding with 2a in the temperature interval 173–253 K with the formation of complex 4a, whereas at ambient temperature, slow isomerization of 2a to (Z)-3-acetylamino-2-butenoate (2b) took place. The investigations with a total of 10 combinations of the catalysts and substrates demonstrated various binding modes that did not affect significantly the enantioselectivities observed in corresponding catalytic reactions and in low temperature hydrogenations of the catalyst–substrate complexes. The monohydride intermediate 10 formed quantitatively when the equilibrium mixture of 2a, 3, and 4a was hydrogenated at 173 K. Its molecular structure including relative stereochemistry was determined by NMR experiments. These results together with the stereochemichal outcome of the low-temperature hydrogenation (99.2% ee, R) and DFT calculations led to the reasonable reaction pathway of the asymmetric hydrogenation of 2a catalyzed by 3. The conceivable catalytic pathways were computed for five combinations of the BenzP*-Rh catalyst and prochiral β-dehydroamino acids 2a,b and 21–23. In most cases, it was found that the pathways involving the hydrogenation of Rh(I) square planar chelate complexes are usually higher in free energy than the pathways with the hydrogen activation prior to the chelate formation. Computed differences in the free energies of the transition states for the double bond coordination stage of the R and S pathways reasonably well reproduce the optical yields observed experimentally in the corresponding catalytic reactions and in the low temperature hydrogenation experiments. To explain extremely high ee’s (>99% ee) in some of the hydrogenations, it is necessary to analyze in more detail the participation of the solvent in the enantiodetermining step.
    ACS Catalysis 12/2013; 4(1):203–219. DOI:10.1021/cs400767e · 7.57 Impact Factor
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    Ilya D Gridnev · Christina Kohrt · Yuanyuan Liu
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    ABSTRACT: DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of enantioselection showed that it takes place via obstructing the proper coordination of the double bond in the S-enantioselective pathway.
    Dalton Transactions 11/2013; 43(4). DOI:10.1039/c3dt52383g · 4.20 Impact Factor
  • C Kohrt · W Baumann · A Spannenberg · H-J Drexler · I D Gridnev · D Heller
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    ABSTRACT: Recently described and fully characterized trinuclear rhodium-hydride complexes [{Rh(PP*)H}3 (μ2 -H)3 (μ3 -H)][anion]2 have been investigated with respect to their formation and role under the conditions of asymmetric hydrogenation. Catalyst-substrate complexes with mac (methyl (Z)- N-acetylaminocinnamate) ([Rh(tBu-BisP*)(mac)]BF4 , [Rh(Tangphos)(mac)]BF4 , [Rh(Me-BPE)(mac)]BF4 , [Rh(DCPE)(mac)]BF4 , [Rh(DCPB)(mac)]BF4 ), as well as rhodium-hydride species, both mono-([Rh(Tangphos)- H2 (MeOH)2 ]BF4 , [Rh(Me-BPE)H2 (MeOH)2 ]BF4 ), and dinuclear ([{Rh(DCPE)H}2 (μ2 -H)3 ]BF4 , [{Rh(DCPB)H}2 (μ2 -H)3 ]BF4 ), are described. A plausible reaction sequence for the formation of the trinuclear rhodium-hydride complexes is discussed. Evidence is provided that the presence of multinuclear rhodium-hydride complexes should be taken into account when discussing the mechanism of rhodium-promoted asymmetric hydrogenation.
    Chemistry - A European Journal 06/2013; 19(23). DOI:10.1002/chem.201204336 · 5.70 Impact Factor
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    ABSTRACT: Transformation of C-F to C-O bond mediated by bifunctional ruthenium and iridium complexes is described. This reaction proceeds through water O-H bond cleavage via metal ligand cooperation in the newly developed 16e bifunctional ruthenium and iridium complexes bearing chiral (S,S)-C6F5SO2-dpen ligand. The 16e Ru amido complex, [Ru{(S,S)-Pfbsdpen}(eta(6)-hmb)] (1a), readily reacted with water at room temperature producing oxometallacyclic compound, (R)-[Ru{kappa(3)(N,N',O)-(S,S)-OC(6)F(4)SO(2)dpen}(eta(6)-hmb)] (3a(R)), as a result of bifunctional water activation followed by ortho-oxometallation via SNAr. Complex 3a(R) can be prepared either from 1a or, more conveniently from its 18e chlorido precursor, complex (R)-[RuCl{(S,S)-Pfbsdpen}(eta(6)-hmb)]. On the contrary, the 16e Ir amido complex, [Cp*Ir{(S,S)-Pfbsdpen}] (2), is kinetically stable toward water at room temperature. Oxometallacyclic compound (R)-[Cp*Ir{kappa(3)(N,N',O)-(S,S)-OC(6)F(4)SO(2)dpen}] (4(R)) was prepared in high yield by the reaction of [Cp*IrCl2](2) with 2 equiv of (S,S)-Pfbsdpen in the presence of KOH under reflux in THF. In either case 3(R) or 4(R) is obtained as a single diastereomer, the structure of which has been determined by single-crystal X-ray diffraction studies in solid state and NMR-analysis in solution. Reaction mechanism was studied by NMR spectroscopy combined with continuum solvent reaction-field density functional theory (DFT) analysis. Experimental studies showed that diastereoselective oxocyclometallation 1a --> 3a(R) proceeds at temperatures >0 degrees C in a stepwise manner through the detectable intermediate, hydroxo complex (R)-[Ru(OH){(S,S)-Pfbsdpen} (eta(6)-hmb)] (6a(R)), which exists in equilibrium with less-populated diastereomer (S)-[Ru(OH){(S,S)-Pfbsdpen}(eta(6)-hmb)] (6a(S)) in 10:1 ratio at -80 degrees C in CD2Cl2. Computational analysis essentially explains the diastereoselectivity in this reaction via a significant difference in the stabilities of the corresponding transition states: although diastereomers 6a(R) and 6a(S) are in equilibrium via complex 1a, only 6a(R) is transformed into 3a(R) via rate-determining Meisenheimer-type transition state.
    Bulletin of the Chemical Society of Japan 05/2013; 86(5-5):557-568. DOI:10.1246/bcsj.20120359 · 2.22 Impact Factor
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    Ilya D. Gridnev · Andrey Kh. Vorobiev
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    ABSTRACT: The relative abundance of various species in the reaction pool of the Soai autoamplification reaction was estimated by large-scale density functional theory (DFT) computations involving calculations of the thermodynamic parameters in solution. Detailed conformational analysis of the macrocyclic tetrameric species formed by dimerization of the Zn–O–Zn–O square dimers and of their ZnPr2i adducts revealed the structural diversification of the homo- and heterochiral species. Homochiral tetramers are exclusively formed in a specific brandyglass conformation with almost orthogonal pyrimidinyl rings that is virtually unaffected by the formation of a ZnPr2i adduct. On the other hand, for heterochiral tetramers the stabilities of brandyglass and layer conformations are approximately equal. The three-dimensional (3D) cavity observed in the ZnPr2i adduct of the homochiral brandyglass tetramer forms an ideal chiral pocket for the coordination of the aldehyde followed by perfectly enantioselective alkylation yielding monomeric alcoholate of the same handedness as the tetrameric catalyst. Similar cavity in the heterochiral brandyglass tetramer is significantly less spacious. Moreover, the cavity practically disappears upon the coordination of ZnPr2i, hence the heterochiral tetramers are excluded from the flow of catalysis that leads to the realization of Frank’s scheme for chiral amplification.
    ACS Catalysis 09/2012; 2(10):2137–2149. DOI:10.1021/cs300497h · 7.57 Impact Factor
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    ABSTRACT: A practical asymmetric C–C bond formation to synthetically useful β-chiral cyclic ketones (>99% ee) using bifunctional chiral amido Ru catalysts under an S/C = 1000, the highest ratio achieved so far in the literature for this class of reactions, is described. The catalytic reactivity decreases in the order of Ru(Msdpen)(hmb) > Ru(Pfbsdpen)(hmb) > Ru(Tsdpen)(hmb) > Ru(PMsdpen)(hmb), where Ru(Pfbsdpen)(hmb) is a newly developed chiral bifunctional catalyst. Complex Ru(Msdpen)(hmb) was identified as the best in terms of reactivity and enantioface selectivity, whereas Ru(PMsdpen)(hmb) gave unsatisfactory results. An importance of the NH proton in the bifunctional catalyst for determining the enantioselectivity has been experimentally demonstrated. Valuable information for the reaction mechanism was accumulated.
    Tetrahedron Letters 07/2012; 53(27-27):3452-3455. DOI:10.1016/j.tetlet.2012.04.100 · 2.39 Impact Factor
  • Yasuharu Hasegawa · Ilya D. Gridnev · Takao Ikariya
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    ABSTRACT: The mechanism of two enantioselective reactions, direct amination of α-cyanoacetates 3 with azodicarboxylates 4 and C–C bond formation reaction of α-cyanoacetates with acetylenic esters 6, catalyzed by chiral bifunctional Ir and Ru complexes, Cp*Ir[(S,S)-N-sulfonated dpen] 1 and Ru[(S,S)-N-sulfonated dpen](η6-arene) 2 (DPEN: 1,2-diphenylethylenediamine) was studied by NMR spectroscopic analysis combined with DFT analysis. Notably, these two reactions using the same chiral amide catalysts 1, 2 and pronucleophile, α-cyanoacetates 3 gave quantitatively the conjugate adducts bearing quaternary chiral carbon centers in excellent enantiomeric excess albeit with the opposite absolute configuration depending on the acceptor molecules 4 and 6. NMR investigation of the reactions between Ir complexes 1a–1c with α-cyanoacetates 3 showed that a stereoselective deprotonation reaction takes place to give an equilibrium mixture of N-bound amine complexes 8 and 9, the former with intramolecular hydrogen bonding and the latter without it, respectively. Computational study revealed the full details of the mechanism of the asymmetric C–N and C–C bond forming reactions catalyzed by the chiral Ir catalyst 1b. In the C–N bond forming reaction, the dimethyl azodicarboxylate 4a undergoes productive bifunctional activation by a non-hydrogen-bonded N-bound complex 9b(re) resulting in the formation of the R-product through the energetically favorable transition state. On the other hand, the linear geometry of the acetylenic ester molecule 6 allows its bifunctional activation with both types of the N-bound complexes: 8b and 9b with and without the intramolecular hydrogen bond respectively. The hydrogen-bond stabilized transition state for the C–C bond formation leading to the S-enantiomer is significantly lower in energy than the corresponding non-hydrogen-bonded transition state leading to the R-enantiomer. Thus, chiral induction of these two reactions is determined by the structures of the acceptor molecules.
    Bulletin of the Chemical Society of Japan 03/2012; 85(3):316-334. DOI:10.1246/bcsj.20110307 · 2.22 Impact Factor
  • Ilya D Gridnev · Elisabetta Alberico · Serafino Gladiali
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    ABSTRACT: The mechanism of asymmetric hydrogenation catalyzed by [Rh(NBD)((R)-PhenylBinepine)(2)]SbF(6)1 has been studied by NMR experiments and DFT computations. Either the low-temperature hydrogenation of the catalyst-substrate adduct 4 or the reaction of solvate dihydride 6 with MAC produced the hydrogenation product with over 99% ee (S).
    Chemical Communications 02/2012; 48(16):2186-8. DOI:10.1039/c2cc17335b · 6.83 Impact Factor

Publication Stats

2k Citations
557.29 Total Impact Points

Institutions

  • 2004–2015
    • Tohoku University
      • Department of Chemistry
      Sendai-shi, Miyagi, Japan
    • University of Bayreuth
      Bayreuth, Bavaria, Germany
    • University of Oxford
      Oxford, England, United Kingdom
  • 2007–2013
    • Tokyo Institute of Technology
      • • Department of Applied Chemistry
      • • Graduate School of Science and Engineering
      Edo, Tōkyō, Japan
    • Okayama University
      • Department of Chemistry
      Okayama, Okayama, Japan
  • 2000–2010
    • Chiba University
      • Department of Chemistry
      Tiba, Chiba, Japan
  • 1992–2010
    • N. D. Zelinsky Institute of Organic Chemistry
      Moskva, Moscow, Russia
  • 1983–2010
    • Lomonosov Moscow State University
      • Division of Chemistry
      Moskva, Moscow, Russia
  • 1995–2001
    • Russian Academy of Sciences
      • Zelinsky Institute of Organic Chemistry
      Moskva, Moscow, Russia
  • 1998
    • Universitätsmedizin Göttingen
      Göttingen, Lower Saxony, Germany
  • 1991–1997
    • Moscow State Forest University
      Mytishi, Moskovskaya, Russia