T. S. Kukhareva

Palladium-catalyzed P-arylation of hydrophosphoryl derivatives of protected monosaccharides

Palladium-catalyzed arylation of hydrophosphorylated protected monosaccharides of the pyranose and furanose series gave the corresponding P-aryl derivatives.

Palladium complexes of phosphorus acid disubstituted ethers. synthesis, structure, catalysis

Abstract Complexes of the type of [Pd2Cl2L4] have been prepared by the reaction of bis-(π-allylpalladium-chloride) with phosphorous acid disubstituted ethers; their structure has been studied by IR- and NMR-spectroscopy and X-ray analysis. The complexes have a dimeric centro-symmetric structure which is usual for bivalent palladium compounds with a slightly distorted flat-square coordination of the central atom. These compounds are active catalysts for hydrogenation of unsaturated compounds. Complexes of biphosphites of sugars can impart asymmetry in hydrogenation of prochiral substrates.

Electrophilic Substitution in the Dihydroquercitin System. Aminomethylation

Treating dihydroquercetin with formaldehyde and amines under conditions of Mannich reaction provided mono- and diaminomethyl derivatives of dihydroquercetin.

Exhaustive acylation of dihydroquercetin

Reaction of dihydroquercetin with acid chlorides of higher and functionalized carboxylic acids was studied with the purpose of creation of new pharmaceuticals.

dihydroquercetin in the reactions with phosphorous acid hexaethyltriamide

The possibility was demonstrated and conditions were developed of a directional phosphorylation of dihydroquercetin flavonoid with phosphorous hexaethyltriamide. The chemical properties of the obtained compounds of trivalent phosphorus are currently under investigation.

Aminomethylation of dihydroquercetin

At present, it is necessary to develop the synthesis of a large number of aminomethylated dihydroquerce tin derivatives of various structure to conduct extended biological testing. We used secondary amines (diisopropylamine and N methylbenzylamine) and primary amine, amy lamine, as the amine components in the Mannich reaction. It should be noted that primary and secondary amines form strong complexes with dihydroquercetin as pale yellow powders. The structure of the complexes was confirmed by 1H and 13C NMR, while the compo sition was corroborated by elemental analysis. It is interesting that the complexes always include only one amine molecule at any flavonoid : amine molar ratios.

Catechol in acylation, phosphorylation, and aminomethylation reactions

The reactivity of dihydroquercetin and catechol flavonoids in acylation, phosphorylation, and aminomethylation reactions was compared. The structure of natural polyatomic phenols was shown to affect markedly their chemical behavior.

Effect of an Inclusion Complex of an Aminomethylated Dihydroquercetin Derivative in Cyclodextrin on Ozone-Induced Oxidation of Fibrinogen

The ability of a water-soluble inclusion complex (KN-14-CD) of an aminomethylated dihydroquercetin derivative (KN-14) in β-cyclodextrin (CD) to inhibit ozone-induced oxidation of fibrinogen was evaluated. KN-14-CD prevented ozone-induced oxidation of fibrinogen and preserved its ability to form clots after the addition of thrombin. The ability of KN-14-CD to prevent oxidative modification of fibrinogen was more pronounced than that of native dihydroquercetin (taxifolin).

Directional Phosphorylation of Dihydroquercetin with Phosphorous Acids Amides

The monophosphorylated products were obtained by phosphorylation of 2,3-dihydroquercetin with phosphorous acid amides. Sulfur addition to these compounds was studied.

2-Polyfluoroalkoxy-1,3,2-dioxaphosphorinanes

Abstract2-Polyfluoroalkoxy-1,3,2-dioxaphosphorinanes and related phosphocyclic compounds were prepared by alcoholysis of 2-amino-1,3,2-dioxaphosphorinanes with polyfluorinated alcohols. Principal chemical properties of the products were studied. For the first time copper complexes of fluorine-containing normal phosphites were prepared. A difference in the ligation of copper with fluorinated and nonfluorinated phosphites was shown.