Major Accomplishments of Zelinsky Institute

KEY BASIC RESEARCH RESULTS OF ZIOC RAS

2013-2014

A unique phenomenon of catalyst surface structuring by applying metal nanoparticles to the carbon support surface under mild conditions in solution and during microwave radiation processing in solid phase was discovered.

(Department of Structural Studies, Laboratory No. 30, Head – Associate Member of RAS V.P. Ananikov)

The first asymmetric organocatalytic reaction in the supercritical carbon dioxide (sc-CO₂) medium was performed. In the catalysis of difunctional tertiary amines containing a squaric acid moieity, triphenylphosphite reacts with a-nitroalkenes to give corresponding b-nitrophosphonates with good yields (59-97%) and excellent enantioselectivity (up to 94%).

(Laboratory No. 11, Head — DSc, Prof. S.G. Zlotin)

A universal method for the synthesis of isoflavones from readily available polyalcoхyallylbenzenes (apiol, dillapiol, and myristicin) isolated from commercial СO₂-extracts from parsley, fennel and vanilla seeds was developed (yield 70-80%).

(Laboratory No. 17, Head – DSc V.V. Semenov).

A method of producing composite membranes based on organometal caracass structures MOF-199 and ZIF-8 on inorganic, metalloceramic or polymer supports was developed.
(Laboratory No. 14, Head - DSc,Prof. L.М. Kustov)

A new type of reactions of donor-acceptor cyclopropanes (DAC) with alkenes under the impact of GaCl₃ where DACs act as formal 1,4-dipoles was found.

(Department of Unstable Molecules and Small-Sized Cyclic Compounds, Head — Academician O.M. Nefedov, Lab. No. 6, Head — Professor Yu.V. Tomilov)

An approach to cyclic peroxides of three different classes, such as tricyclic monoperoxides, bridged tetraoxanes and two isomeric ozonides, based on the heteropolyacids-catalyzed reaction of β, δ-triketones with H₂O₂was proposed. This is the first example of preparing an ozonide cycle by peroxidation of carbonyl compounds.

(Laboratory No. 13, Deputy Head – DSc А.О. Terentiev, PhD I.А. Yaremenko)

A comprehensive study of the multicomponent process mechanisms has led to a new efficient “one-pot” and “on-water” electrocatalytic method of the cascade transformation of salicylic aldehydes and three malononitrile molecules to substituted tri- and tetracyclic chromeno[2,3-b]pyridine systems with 75-90% yield by substance and 375-450% yield by current.

(Department of Unstable Molecules and Small-Sized Cyclic Compounds – RAS Full Member O.M. Nefedov, Lab. No. 1, Head — RAS Full Member M.P. Egorov, DSc M.N. Elinson)

A new strategy of the one-step synthesis of condensed 1,2,5-selenadiazoles from respective 1,2,5-thiadiazoles was proposed and implemented. It allowed high yields of a number of new heterocyclic systems that are promising as the sources of stable anion radical salts — molecular electricity conductors and magnetics.

(Laboratory No. 31, Head — DSc, Prof. О.А. Rakitin)

A reagent acting as a difluoromethylene-bis equivalent (carbanion) was proposed.

(Laboratory No. 8, Head – DSc А.D. Dilman)

Numerical simulation and cyclic voltammetry methods have shown that the factor determining selectivity of electroreduction of arylhydroxylamines is a previously unknown reaction of hydroxide anion elimination from anion radicals of these compounds that initiates competitive processes of the formation of hydrazo and azo derivatives. Their yield ratio dramatically changes while switching from electroanalytical methods to the electrolysis with the controlled potential.

(Laboratory No. 50, Head – DSc А.S. Mendkovich, in cooperation with DSc, Prof. V.P. Gultiay and Yaroslavl State University)

On the basis of a mature concept of the interlayer dynamics of active sites, substantiation was proposed for three baseline models that underlie modern ideas about the mechanism of the hydrotreating catalysis by transition metal sulphides; boundary conditions of these models functioning were identified.

(Laboratory No. 38, Head — DSc V.М. Kogan, in cooperation with Lab. No. 40, Head – Associate Member of RAS A.L. Lapidus and Samara State Technical University)

A novel reaction unparalleled in oganic chemistry, viz. a rearrangement of pyranosides to furanosides in the conditions of acid-catalyzed exhaustive sulfation and under the action of SO₃ amine complexes, was discovered.

(Laboratory No. 52, Head – Associate Member of RAS N.E. Nifantiev, PhD V.B. Krylov).

Synthetic methods were developed to prepare high energy organic compounds of a new class, vis. derivatives of azoxyfurazanilfuroxanes, with exceptionally high energy performance.

(Laboratory No. 12, Head – DSc, Prof. О.А. Lukianov)

A convenient method for the synthesis of a wide range of complexes of soluble metals and metal nanoparticles from the single precursor avoiding complex experimental procedures was developed.

(Laboratory No. 30, Head – Associate Member of RAS V.P. Ananikov)

For the first time a highly selective method for the synthesis of asymmetrical tienothiophenes via a double “domino” reaction using “dilution effect” was developed.

(Laboratory No. 25, Head – DSc, Prof. А.М. Shestopalov)

Unique reactivity of β, δ-triketones in a reaction with H₂O₂was discovered: among numerous possible pathways of their transformation one way predominates and leads to previously unknown tricyclic structures containing peroxide, monoperoxyketal and ketal fragments.

(Laboratory No. 13, DSc А.О. Terentiev, PhD I.А. Yaremenko)

An efficient sulfur resistant catalyst of the synthesis of higher alcohols based on molybdenum sulphide promoted by cobalt and potassium was developed.

(Laboratory No. 38, Head — DSc, V.М. Kogan, in cooperation with Lab. No. 40, Head – Associate Member of RAS А.L. Lapidus, and Samara State Technical University).

For the first time has been found a new type of reactivity of donor-acceptor cyclopropanes, which, under the impact of GaCl3, act as sources of even 1,2- and 1,4-dipoles responsible for the formation of four- and six-membered carbocycles.

(Department of Unstable Molecules and Small-Sized Cyclic Compounds, Head – RAS Full Member O.M. Nefedov, Lab. No. 6, Head – DSc, Prof. Yu.V. Tomilov)

Pioneering heterogeneous catalytic oxidation of benzene to phenol by nitrous oxide on a zeolite catalyst (HZSM-5) under supercritical conditions (280-420°C, P = 60-180 atm) was performed. Productivity of HZSM-5 increases 10-fold as compared to a gas phase process, stability of its operation is higher and selectivity (phenol) is above 90%.

(Group of RAS Full Member V.V. Lunin, Dsc V.I. Bogdan)

Previously unknown synergistic effect during selective reduction of nitrogen oxides on composite catalysts [zeolite + oxide component] was detected.

(Laboratory No. 35, Head – Dsc, Prof. А.Yu. Stakheev)

Fucoidan with a unique structure was isolated in high yield from Punctaria plantaginea.

(Laboratory No. 21, group of Prof. А.I. Usov, PhD М.I. Bilan, in cooperation with Lab. No. 30, Head – Associate Member of RAS V.P. Ananikov, Dsc А.S.Shashkov)

A new general methodology of fluoroanilination of N-, O-, C- and P-nucleophilic substrates was developed on the basis of carbine fluorochlorocyclopropanation of alkenes and catalytic skeletal transformatios of gem-fluorochlorocyclopropanes.

(Department of Unstable Molecules and Small-Sized Cyclic Compounds, Laboratory No. 5, Head – RAS Full Member О.М. Nefedov, PhD N.V. Volchkov).

Major Accomplishments on cover pages of international journals

Cover picture of ”Journal of the American Chemical Society”. The paper was published under the title “Efficient General Procedure to Access a Diversity of Gold(0) Particles and Gold(I) Phosphine Complexes from a Simple HAuCl4 Source. Localization of Homogeneous/Heterogeneous System’s Interface and Field-Emission Scanning Electron Microscopy Study”. The authors are S.S. Zalessky, A.E Sedykh, A.S. Kashin, and V.P. Ananikov. Laboratory of Metal-Complex and Nanoscale Catalysts.
Cover picture of ”Chemical Reviews” . The paper was published under the title “Miniaturization of NMR Systems: Desktop Spectrometers, Microcoil Spectroscopy, and "NMR on a Chip" for Chemistry, Biochemistry, and Industry”. The authors: S. Zalessky, E. Danieli, B. Blumich, and V. Ananikov. Laboratory of Metal-Complex and Nanoscale Catalysts.
Cover picture of “Organometallics”.The paper’s title “Toward the Ideal Catalyst: From Atomic Centers to a “Cocktail” of Catalysts The authors: V. Ananikov and I. Beletskaya.
Coverpicture of ”Chemical Reviews”. The paper’s title “Characterization of Molecular Systems and Monitoring of Chemical Reactions in Ionic Liquids by Nuclear Magnetic Resonance Spectroscopy“. The author – V. Ananikov.
Cover picture of ”Chemistry – A European Journal”. The paper’s title “Catalytic Hydrofunctionalization of Alkynes through PH Bond Addition: The Unique Role of Orientation and Properties of the Phosphorus Group in the Insertion Step”. The authors: V. Ananikov, А. Makarov, and I. Beletskaya
Cover picture of “Chemical Reviews”. The paper’s title “Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formation via Cross-Coupling and Atom-Economic Addition Reactions” The authors: I. Beletskaya and V. Ananikov.

Cover picture of ”Advanced Synthesis & Catalysis”. The paper’s title “Acid-Free Nickel Catalyst for Stereo- and Regioselective Hydrophosphorylation of Alkynes: Synthetic Procedure and Combined Experimental and Theoretical Mechanistic Study”. The authors: V. Ananikov, L. Khemchian, I. Beletskaya, and Z. Starikova.
Cover picture of “Mendeleev Communications”. The paper’s title “Mechanistic insight into organic and catalytic reactions by joint studies using mass spectrometry and NMR spectroscopy”.The authors: P. Beliakov, V. Kadentsev, А. Chizhov, N. Kolotyrkina, А. Shashkov, and V. Ananikov.
Cover pictureof “European Journal of Inorganic Chemistry”. The paper’s title “Catalyst Leaching Leading to New Catalytic Reactions – the Synthesis of Cyclic Vinyl Sulfides and Vinyl Selenides”. The authors: V. Ananikov, К. Gaiduk, I. Beletskaya, V. Khrustalev, and М. Antipin.
Cover picture of “European Journal of Organic Chemistry”. The paper’s title “Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions”. The authors: I. Beletskaya and V. Ananikov.
Cover picture of ”Chemistry – A European Journal”. The paper’s title “Two Distinct Mechanisms of Alkyne Insertion into the Metal–Sulfur Bond: Combined Experimental and Theoretical Study and Application in Catalysis”. The authors: V. Ananikov, К. Gaiduk, N. Orlov, I. Beletskaya, V. Khrustalev, and М. Antipin.