ABOUT

 

Laboratory of Coordination Chemistry at the Department of Chemistry of Ryazan State University named for S. Yesenin was formed by the decision of the Academic Council of the University in December 1998 on the basis of the coordination design group that had existed since 1991.The main area of ​​scientific research in the laboratory is the complexation and use of chiral phosphorus-containing ligands in asymmetric catalysis, which have a pronounced π-acidity of the phosphorus donor center. Being at the junction of several modern chemical disciplines - inorganic, organoelement chemistry and chemistry of catalytic processes, it provides the possibility of obtaining enantiomerically pure biologically active compounds. In other words, the unique metal complex catalysts being developed are many times accelerating the synthesis of practically significant rare substances - pharmaceuticals, plant protection products, and bioregulators. Just as importantly, they can be produced in the stereomeric forms necessary for man and nature. The consequence of this approach is that if the results are introduced into the industry, the production costs are almost halved and there is no toxic effect on the environment and the human health. In addition, phosphite ligands offered for use are 50-55 times cheaper than commercially available phosphine stereoselectors.

 

The actual scientific problem is to design and synthesize earlier unavailable and modular diamidophosphite chiral ligands, as well as to test them in the Pd-, Rh-, and Ir-catalyzed enantioselective transformations. The coordination behavior of obtained chiral inducers with respect to rhodium(I), iridium(I), and palladium(II) are determined. New ligands are used in a wide spectrum of asymmetric catalytic reactions, including those opening the way to building blocks of valuable bioactive compounds. The synthetic availability and variable structure make such ligands exceptionally convenient for the study of asymmetric induction in metal complex-catalyzed reactions, including the structure and stereochemical features of chiral ligands – complexation regularities – performance in enantioselective organic reactions relationship. The activity and stereoselectivity of metal complex catalysts largely depend on the correct strategy in the design of corresponding chiral ligands, primarily, phosphorus-containing ones whose numerous representatives have been used in asymmetric transformations. Nevertheless, the vast majority of such ligands when being a part of corresponding metal complexes can with certain enantioselectivity catalyze chemical transformations of only one type or only specific reaction. Sufficiently versatile (so-called privileged) ligands are few and their high cost restricts their wide application in practice. In general, further advances in the design and synthesis of chiral phosphorus-containing ligands are associated with a) a growing demand for new efficient phosphorus-containing chiral inducers which can be obtained with ease from enantiopure starting compounds, b) a need to increase the array of experimental data significant for determination of asymmetric induction (intramolecular diastereoselectivity) regularities in metal catalysis, and c) the importance of overcoming patent restraints upon the use of some known ligand series. Among ligands of phosphite nature, diamidophosphites (PON2) are actively developing promising class of chiral inducers. The choice of topical catalytic processes is governed by the necessity for a comprehensive study of the asymmetrizing capability of novel ligands and, correspondingly, contemplates the use of classical model reactions as an estimating tool to determine the efficacy of new chiral inducers. The scientific research also contemplates the study of catalytic reactions for which it is difficult to achieve high enantioselectivity, non-trivial catalytic processes, and practically valuable transformations opening the way to valuable bioactive compounds.

 

Head of Laboratory

Professor Konstantin N. Gavrilov was born in 1963 in Kursk, Russia. He graduated from Ryazan State University in 1985. In 1987-1990 he was a Ph.D. student at the Institute of Organic Chemistry (Russian Academy of Sciences) under the supervision of Professor E. I. Klabunovsky and Professor E. E. Nifantyev.  In 1991 he obtained a Ph.D. degree in Organic Chemistry studying the synthesis and application of phosphite-type ligands based on amino alcohols and joined Ryazan State University as Assistant Professor at the Department of Chemistry. In 1998 he obtained a Doctor of Chemical Sciences degree (Russian analog of Habilitation) involving the chemistry of rhodium and palladium complexes and became a Full Professor of Inorganic Chemistry. Now Konstantin Gavrilov is Head of Laboratory on Coordination Chemistry of Ryazan State University. He is the author and co-author of more than 180 publications including 5 reviews. The main field of scientific interests is development of new chiral organophosphorus ligands (with particular emphasis on phosphite-type ligands), and investigation of their catalytic applications and coordination behavior. He has been a supervisor of 13 postgraduate studies. He has the Award of the Ministry of Education and Science of the Russian Federation "For the development of research work of students" in 2005. Since 2015 he is Honorary Worker of Higher Professional Education.

 

Department of Chemistry, Ryazan State University, 46, Svoboda Str., Ryazan, 390000, Russia. Telephone: +7 4912 28 0580.

E-mail: k.gavrilov@365.rsu.edu.ru

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Scientific collaboration

During its existence, the laboratory carried out creative partnerships with Russian and foreign scientific centers - INEOS RAS named for A.N. Nesmeyanov (Laboratory for Stereochemistry of Sorption Processes), IOС RAS named for N.D. Zelinsky (IR spectroscopy group), IBC RAS named for M.M. Shemyakin and Yu.A. Ovchinnikov (mass spectrometry group), Institute of Chemistry of the Academy of Sciences of Moldova (Kishinev, Moldova), Leibniz Institute for Catalysis (Leibniz-Institut fur Katalyse an der Universitat Rostock eV, Germany), Coal Institute (Max-Planck-Institut fur Kohlenforschung, Mülheim, Germany), University of Geneva (Departement de Chimie Organique, Universite de Geneve, Switzerland). Currently, cooperation with M.V. Lomonosov Moscow State University (Department of Organic Chemistry), Moscow Institute of Physics and Technology (Department of Molecular and Biological Physics), IPCE RAS named for A.N. Frumkin, University of Erlangen (Friedrich-Alexander-Universität Erlangen-Nürnberg, Germany). This cooperation provides the basis for joint research projects, joint publications, the providing of expensive compounds, and access to analytical instruments, electronic libraries and databases. The most successful graduates of the RSU go to graduate school at the Department of Chemistry of the RSU and the Department of Organic Chemistry of the Moscow State University.

Awards and academic degrees

Over the years, students and graduate students of the laboratory were awarded scholarships and prizes of the Academic Council of the RSU, the head of the Administration of the Ryazan Region, the head of the Administration of Ryazan, the scholarships of the President of the Russian Federation and the Government of the Russian Federation, state scientific scholarships, scholarships from the Soros Foundation, DuPont, Haldor-Topse and Bayer, as well as scholarships of the International Charitable Scientific Foundation named for K.I.  Zamaraev. Laboratory developments were awarded with a diploma of the VIII Moscow International Salon of Innovations and Investments (2008). The laboratory staff became laureates of the European Academy competitions for young scientists of Russia in the "Chemistry" section and the International Charity Scientific Fund named for K.I. Zamaraev. Over the past years, they have repeatedly won prizes of the Governor of the Ryazan Region for young scientists, and they have been winners of the "U.M.N.I.K" program. Since 1998, the laboratory staff defended 14 Ph.D. in the Inorganic Chemistry, Chemistry of Organoelement Compounds and Organic Chemistry.

Financial support

In 2008-2019 the scientific work of the laboratory was carried out with the financial participation of:

• INTAS international grant “A new generation of stereoselectors for metal complex catalysis”

• A grant from the President of the Russian Federation for state support of young Russian scientists “Asymmetric catalytic substitution and addition with the participation of a new generation of phosphite stereoselectors”

• RFBR grant “Novel P,P-bidentate stereoselectors for C *-C bonds formation enantioselective reactions”

• RFBR grant “P*- and P-donor chiral phosphocyclanes in Pd-catalyzed asymmetric reactions”

• RFBR grant “Phosphorylated amides of diamines and aminoalcohols as promising chiral inductors for metal complex catalysis”

• RFBR grant “Asymmetric catalytic synthesis of α-aminophosphonates involving chiral oxalamides and their phosphoderivatives”

• RFBR grant “Obtaining of medicinal drugs using asymmetric metal complex catalysis”

• RSF grant “Chiral phosphites based on metalloporphyrins: synthesis, complexation, photophysical properties and application in asymmetric catalysis”

• RSF grant “Supramolecular metal complex systems based on phosphorylated pseudodipeptides as new asymmetric catalytic materials”

• RSF grant “Development of efficient asymmetric catalytic systems based on novel phosphite-nature chiral P,S-ligands”

• several grants from the Ministry of Education and Science of the Russian Federation and the German DAAD Academic Exchange Service under the Mikhail Lomonosov program

• program “Member of the Youth Scientific and Innovation Competition” ("U.M.N.I.K").

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Рязанский государственный университет имени С.А. Есенина