To Oleg Shishkin

Dr.Sc. in Chemistry, Acting General Director of the SSI “Institute for Single Crystals” of the National Academy of Sciences of Ukraine, Head of the Department of X-ray Diffraction Studies and Quantum Chemistry, an extraordinary man – Prof. Oleg Valeryevich Shishkin who passed away at the age of 47

Hydantoins Derived from Ketopinic and 4-camphorcarboxylic Acids

Diastereospecific formation of hydantoins from ketopinic and 4-camphorcarboxylic acids under Bucherer-Bergs reaction conditions has been investigated. The easiness of this transformation provides a straightforward synthetic pathway to enantiopure conformationally rigid amino acids derivatives, as well as functionalized hydantoins, starting from inexpensive and easily available natural camphor

Reaction of pyrido[2,1-a]isoindole with 1,4-naphtoquinone and study of the product by spectroscopic methods

Key role of the electronic structure of condensed isoindols in the way of the rearrangement was shown. Influence of the dienophile manifests in the requirement of the cyclic form of the dienophile itself. In the reaction of pyrido[2,1-a]isoindole with naphtoquinone rearrangement product of the first type was obtained and its structure was proven by spectral methods. Spectral criteria for the rearranged adducts of the first type for the pyrido[2,1-a]isoindole in the 13C NMR spectra were established. Products of reactions with naphthoquinone, 4-fluoro-, 2,5-difluorophenylmaleimides were isolated and characterized: (2E)-2-[(1,4-dihydroxy-2-naphthyl)(2-pyridin-2-ylphenyl)methylene]-4-hydroxynaphthalen-1(2H)-one, (3E)-1-(4-fluorophenyl)-3-[[1-(4-fluorophenyl)-2,5-dioxopyrrolidin-3-yl](2-pyridin-2-ylphenyl)methylene]pyrrolidine-2,5-dione, (3E)-1-(2,4-difluorophenyl)-3-[[1-(2,4-fluorophenyl)-2,5-dioxopyrrolidin-3-yl](2-pyridin-2-ylphenyl)methylene]pyrrolidine-2,5-dione

7th International Scientific Conference in Chemistry ‘Kiev-Toulouse’

7th International Scientific Conference in Chemistry Kiev-Toulouse was held June 2-7, 2013 at the Department of Chemistry of the National Taras Shevchenko University of Kiev (KNU)

Isoindole and isomeric heterocyclic donating substituents in ruthenium(II)nitrosyl complexes with large first hyperpolarizabilities and potential two-photon absorption capabilities: a computational approach

A set of 22 ruthenium nitrosyl complexes of general formula [RuII(L)Cl2(NO)]+ is investigated computationally by the density functional theory. L is a terpyridine ligand substituted by different R isomers of formula C12H8N, either indole, isoindole, or carbazole, proposed as alternative donors to the electron-rich fluorene substituent. The computed resulting nonlinear optical (NLO) properties are found to strongly depend on the isomer. While the ruthenium complexes exhibit modest efficiencies at the second-order (two-photon absorption) level, some of the R isomers lead to complexes of enhanced capabilities in first order (b) nonlinear optics. The synthetic feasibility of these ligands is discussed

Towards fluorescent indolyl-carbo-benzenes

The C18 macro-aromatic carbo-benzene core is a strong chromophoric unit resembling the porphine ring which is prone to quench the emission of fluorophoric substituents. Within the aim of preparing fluorescent carbo-benzenes (and carbo-cyclohexadiene parents) for measurement of their two-photon absorption cross-section by the TPEF method, several indole derivatives were devised and anchored to the C18 macrocycle either directly, p-phenylogously or ethynylogously. Synthesis methodology and spectroscopical measurements are presented in a comparative prospec

Reaction of 1-aminoisoindole with 1,4-naphthoquinone and study of the product by spectroscopic methods.

In our previous researches we have shown, that 1-aminoisoindole, which exists predominantly in isoindoline tautomeric form, can undergo [4+2]-cycloaddition reactions with maleimides according to the Curtin-Hammet principle. We continued to study this reaction, but with another dienophile – 1,4-naphtoquinone. In this case, the reaction does not stop when the bis-Michael adduct is obtained, but continues with the formation of a more complex compound, the structure of which we have studied by two-dimensional NMR spectroscopic methods

Reaction of 1-aminoisoindole with methyl 4-chloro-3-oxobutanoate

Condensation of bifunctional 1-aminoisoindole with bis-electrophilic methyl 4-chloro-3-oxobutanoate undergoes regioselectively to afford 2-(chloromethyl)-2-hydroxy-2,6-dihydro­pyrimido[2,1-a]isoindol-4(3H)-one. The structure of the reaction product was unambiguously established by HMQC and HMBC heteronuclear correlations. The functionalization of the synthesized compound by reactions with a series of aliphatic amines was carried out

Michael addition of heteronucleophilic substances to N – Ar substituted maleimides: green approach

A new method for the preparation of the adducts of aromatic hetero nucleophiles (NH, SH, ОH) to the activated C=C bond of N-aryl-substituted maleimides using Michael reaction was developed. A possibility to obtain mono-adducts was demonstrated for 2-aminopyridine derivatives. It was proven that in the case of amino phenols, which possess three potential nucleophilic centers, only the addition to amino group occurs. Utility of the method for the formation of C–C bond in Michael reaction was also demonstrate

6-Oxyindan-1-ones with dipeptide chains

Through N-acylation of a- or b-amino acid units by 2-(3-oxo-2,3-dihydro-1H-inden-5-yloxy)acetic acid using the method of N-hydroxysuccinimide esters new dipeptide indan-1-one derivatives were obtained. In general, the direct interaction of the acetic carboxyl group of the substrate with the amino group of the a- or b-dipeptide is a more productive strategy than the sequential peptidic condensation of the two amino acids