Biography
Yuri Varshavsky earned his PhD degree in 1965 at the Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia. During the period 1967-1996, he was Head of laboratory at the Lebedev Institute of Synthetic Rubber, St. Petersburg, Russia. From 1997-2013, he worked as Head of Research Group at the Department of Chemistry at St. Petersburg State University. Having retired in 2014, he is currently involved, as an independent scholar, in the interpretation of experimental data obtained earlier by him and his colleagues. He has published more than 200 papers in peer-reviewed journals, delivered over 30 presentations at the international conferences, and received 10 patents. He also published (in co-authorship with M. I. Gelfman) a biography book about his scientific mentor, academician A A Grinberg. (“Naukaâ€, Leningrad, 1974). His research interests are focused on the coordination chemistry of rhodium.
Abstract
13C NMR spectrum of [Rh(Acac)(CO)2] (1) in solution (CDCl3) contains four doublet signals (multiplicity/ chemical shift, ppm/ nJ, Hz/ number of nuclei/ group assignment): d/ 183.8/ 73.0/ 2C/ carbonyl ligands; d/ 187.4/ ~1 / 2C/ CO(Acac); d/ 101.8/ 2.6/ 1C/ CH; d/ 27.1/ 1.1/ 2C/ CH3. 13C MAS NMR spectrum of the polycrystalline 1 displays 7 signals: d/ 185.4/ 70.7/ 1C and d/ 184.0/ 72.4/ 1C/ carbonyl ligands; s/ 188.1/1C and s/ 185.8/ 1C/ CO(Acac); s/ 100.3/ 1C/ CH; s/ 27.7/ 1C and s/ 27.0/ 1C/ CH3. (They appear as 8 peaks – see Fig. 1). The results support our assumption based on the IR data that molecule 1 loses its C2v symmetry on passing from the solution into the crystal (Rubailo A I, Selina V P, Varshavskii Yu S Soviet J. Coord. Chem. 14 (1989), p. 531). Inequivalence of carbonyl ligands in the molecule 1 may result from difference in their close surroundings in the crystal. For example, the contacts O•••H–C of two CO ligands to methine group of the neighboring molecule in the adjacent stack (denoted with prime) are markedly different: (O)•••(H)\' 2.72 Å; (O)•••(C)\' 3.65 Å; angle(O)(H)\'(C)\' 164.9º for one CO ligand, and (O)•••(H)\' 4.38 Å; (O)•••(C)\' 5.00 Å; angle (O)(H)\'(C)\' 126.4º for the other.rnNMR studies were performed at the Centre for Magnetic Resonance, St. Petersburg State University.
Biography
Abstract
Such N-heterocycles as indoles, pyrroles and imidazoles are a type of nitrogen containing molecules\r\noccurring in numerous natural and biologically active compounds with a wide range of pharmaceutical\r\nproperties. Amines are ubiquitous in nature. Due to prevalence of amines in therapeutics, as well as in\r\nthe production of dyes, solvents, agrochemicals, and fine chemicals, the formation of carbon-nitrogen\r\nbonds is of tremendous unportance. Hydroamination, the net addition of amino group and hydrogen\r\natom across a carbon-carbon multiple bond, represents a direct approach to access amines from alkene\r\nand alkyne precursors. On the other hand, it is well known that ferrocene is a considerable\r\npharmacophore.\r\nWe hope that introduction of ferrocenyl group into the biologically active molecules will reveal the\r\nenhanced biological activity. We have developed a simple, efficient catalyst-free addition of indoles\r\nand pyrroles to ferrocenylnitroethylene Fc-CH=CH-NO2 (Fc=ferrocenyl), with formation of 3-(2-nitro-\r\n1-ferrocenyl)-indole and 2-(2-nitro-1-ferrocenyl)-pyrrole. Because of the presence of the nitro group,\r\nthese products can be readily transformed into a variety of functionalities.\r\nAs part of our current studies on the reactions of ferrocenyl-containing electron-deficient alkynes and\r\nalkenes [1,2] with N-heterocycles and amines, we found that alkyne Fc-C≡C-CN reacts with 1-\r\nmethylimidazole to give corresponding C(2)-vinylated derivative-3-(1-methyl-imidazole-2-yl)-3-\r\nferrocenyl-2-propenenitrile.\r\nAcetylenic nitrile Fc-C≡C-CN smoothly adds amines-diethylamine, morpholine, pyrrolidine and\r\nothers, with formation of the corresponding enaminonitriles.\r\nWe are grateful to the Shota Rustaveli National Science Foundation (Grant YS15_2.1.4_110) for\r\nsupport of this work.