[Glycosilated derivatives of substituted hydroxylamine. II. Phase transfer synthesis and investigation of glycosyl transfer reaction of glucosaminides of substituted hydroxylavine].

1-(2-Acetamido-3,4,6,-tri-O-acetyl-2-deoxy-beta-D-glucopyranosyloxy)-benzotriazole reacted in boiling dichloromethane, in the presence of Luis acids as a promotors with primary and secondary aliphatic and cycloaliphatic alcohols and diisopropilidene galactose with alkyl-O-1,2-trans-glucosaminides formation. It was shown that the other glucosaminides of substituted hydroxylamine are not participated in this reaction. Structures of glucosaminides were identify by 1H-NMR-spectroscopy and comparison with known compounds.

[Features phase transfer catalytic glycosylation of aromatic hydroxy acids].

The catalytic phase transfer reactions of per acetylated alpha-D-glucosaminyl chloride with isomeric hydroxybenzoic, 1-hydroxy-2-naphthoic acids in solid potassium carbonate--acetonitrile were studied. It was found that the composition and yields of reaction products are determined by the nature of the source ofcarboxylic acids, lipophilic phase transfer catalyst, temperature. For the first time found that the O-beta-glycosyl esters of ortho-hydroxyaromatic acids in the presence of potassium carbonate can anomerizovatsya in 1,2-cis derivatives. The structure of the synthesized compounds proved 1H NMR spectroscopy. In in vivo experiments it was established that glycosyl esters of salicylic acid and per acetylated 2-carboxy phenylglucosaminide exhibit analgesic activity similar to aspirin.

[Synthesis and antimicrobial ivestigation of 8-quinolinols glucosaminides].

In the phase transfer system solid calcium carbonate--acetonitrile per acetylated O-beta-D-glucosaminides of 8-quinolinol, 2-methyl-8-quinolinol and 5-chloro-8-quinolinol were synthesized. Zemplen deacetylation was led to corresponding trioles. Obtained O-beta-D-glucosaminides were identified with 1H-NMR spectroscopy. Antimicrobial activity of deacetylated forms has been studied in a test of inhibition of bioluminescence of marine luminescent bacteria Vibrio fischeri F1 and method of the serial breeding on the museum steams of Escherichia coli, Agrobacterium tumefaciens, Bacillus cereus, Micrococcus luteus. It was established that glycosylation decrease antimicrobial activity in comparison with non-glycosilated 8-quinolinols.

[Glycosides of hydroxylamine derivatives. I. phase transfer synthesis and study of isatine-3-oximes glucosaminides influence on bacterial luminescence].

In the phase transfer system solid calcium carbonate-acetonitrile, per acetate alpha-D-glucosaminilchloride glycosilate easily deprotoned isatine-3-oximes hydroxyl groups. It was found that the presence in the reaction mixture a catalytic amounts of 15-crown-5 accelerated the process twice. Obtained O-beta-D-glucosaminides were identified with 1H-NMR spectroscopy. Features of synthesized compound's NMR spectra are discussed in comparison with those of another N-acetylglucosamine 1-O-derivatives. The biological activity of the some oximes with different substituents in isatin residuum has been studied in a test of inhibition of bioluminescence of marine luminescent bacteria Photobacterium leiognathi Sh12. The nature of N-substituent of isatin fragment and 5-substituent of isatin main structure is compared with glycosides ability to suppress bacterial luminescence.

[Synthesis of heteroaromatic N-beta-glycosides of N-acetylghicosamine under phase transfer conditions. III. 1,2,4-triazoIin-3-ones glucosaminides].

The catalytic phase transfer reactions of 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-a-D-glucopyranosyl chloride with thiosubstituted 4-phenyl-5-R-thio-Delta2-1,2,4-triazolin-3-ones in solid alkali-organic solvent and in aqueous alkali-organic solvent were studied. The main products ofglucosaminilation reaction are the appropriate N-beta-glucosaminides. The effect of reaction conditions on the yield and composition of products formed was elucidated on the example of the reaction alpha-D-glucosaminyl chloride with 5-methylthio-4-phenyl-Delta2-1,2,4-triazolin-3-one. The optimal conditions of phase transfer glycosylation were established. N-1,2-trans-grycosidic bond formation was proved by 1H NMR and IR data as well as a comparison with spectral data obtained previously for the glycosides of similar structure.

[Neuro- and psychotropic activity of N-uronoylamino acids and N-uronoylpeptides].

Peculiarities of rat behavior were studied on a series of experimental stress models after systemic administration of new N-uronoyl derivatives of amino acids. The psychotropic effect was shown to be determined by the nature of the amino acid fragment. N-(l,2:3,4-di-O-isopropylidene-alpha-D-galactopyranuronoyl)-glycylglycine exhibited a more pronounced anxiolytic effect than pyracetam, whereas N-(l,2:3,4-di-O-isopropylidene-alpha-D-galactopyranuronoyl)-glycylglutamic acid is a stronger antidepressant than amitriptyline. Mechanisms of the psychotropic effects of the examined derivatives are discussed.

[Synthesis of heteroaromatic N-beta-glycosides of N-acetylglucosamine under phase transfer conditions: II].

Regioselective N-beta-glucosamination of various unsubstituted or C4-, C5-, or C6-monosubstituted indolin-2-ones under phase transfer conditions was studied. The regioselectivity was unambiguously proved by (1)H NMR spectroscopy and X-ray analysis. The presence of a substituent at C7 of the aromatic ring leads to the formation of either a mixture of isomeric N-beta- and O-beta-D-glucosaminides or only oxazoline and/or 2-acetamidoglycal irrespective of the reaction conditions.

[Interferon-stimulating activity of muramoyl dipeptide glycosides].

The uninvestigated interferon (IFN)-inducing capacity of glycoside derivatives of N-acetylmuramoyl-L-alanyl-D-isoglutamine (MDP) has been studied. Most MDP glycosides tested in vitro were more active than the reference preparation MDP. Under the in vivo conditions three studied preparations: MDP, a-heptyl-MDP and beta-(2-methyl-3-phenylchromonyl-7)-MDP stimulated production of considerable amount of circulating IFN that evidences for the promising character of their further investigation as preparations immunostimulators.

[Synthesis of heteroaromatic N-beta-glycosides of N-acetylglucosamine under the conditions of phase transfer catalysis: I. Glucosaminides of 2-oxobenzazoles].

Glycosylation of methylbenzoxazolone-2 and benzothiazolone-2 with the full acetate of alpha-D-glucosaminyl chloride in the phase transfer systems investigated (solid-organic solvent and aqueous alkali-organic solvent) regioselectively leads to the corresponding N-beta-D-glucosaminides, which is proved by 1H NMR spectroscopy and X-ray analysis.

[Glycosylation of 5-Phenyl-1,3,4-oxadiazole-2-thiol with alpha-D-glucopyranosyl chloride under phase transfer conditions].

5-Phenyl-1,3,4-oxadiazole-2-thiol is glycosylated easily and in high yields with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha-D-glucopyranosyl chloride in the presence of catalytic amounts of aliphatic and aromatic crown ethers under phase transfer (solid-organic solvent) conditions. The reaction rate and the ratio of the resulting N- and S-regioisomers depend on the catalyst nature.

[A synthesis of heteroaromatic S- and N-beta-glycosides of N-acetylglucosamine under phase transfer conditions].

The use of crown ethers for a phase transfer-catalyzed synthesis of heteroaromatic glycosides of N-acetylglucosamine was studied. The solid-liquid system and the catalysis by 15-crown-5 were found to provide for both a 100% conversion of the alpha-D-glucosaminyl chloride peracetate and a high reaction rate. The interaction of alpha-D-glucosaminyl chloride peracetate and oxadiazole and triazole mercapto derivatives capable of thiol-thione tautomerism carried out at room temperature in acetonitrile in the presence of anhydrous potassium carbonate and crown ethers was shown to lead to both S- and N-glycosides. The structures of the compounds synthesized were confirmed by X-ray analysis and 13C and 1H NMR spectroscopy.

[A phase-transfer glucosamination of phenols catalyzed by polyethylene glycol].

Glycosylation of phenols with alpha-D-glucosaminyl chloride peracetate catalyzed by polyethylene glycol (PEG) was carried out in a solid-liquid phase transfer system at room temperature. The results were compared with those previously obtained for the catalysis with various crown ethers. The catalytic activity of PEG in this reaction was found to be comparable with those of 15-crown-5 and aromatic crown ethers. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2005, vol. 31, no. 3; see also http://www.maik.ru.

[Aromatic crown ethers as phase transfer catalysts in the synthesis of N-acetylglucosamine beta-aryl glycosides]. / Aromaticheskie kraun-éfiry kak katalizatory sinteza beta-arilglicozidov N-atsetilgliukozamina v mezhfaznykh usloviiakh.

The crown ether-catalyzed glycosylation of phenol, 4-methoxyphenol, and 4-nitrophenol was studied under phase transfer conditions in solid-liquid system. The asymmetric dibenzocrown esters are superior to [3.3]dibenzo-1 8-crown-6 and 15-crown-5 in the catalysis of these reactions. The English version of the paper: Russian Journal of Bioorganic Chemistry, 2004, vol. 30, no. 3; see also http://www.maik.ru.

[N-acetylmuramyl-L-alanyl-D-isoglutamine glycosides. Effect of glycoside center configuration and aglycone nature on biological activity]. / Glikozidy N-atsetilmuramoil-L-alanil-D-izoglutamina. Vliianie konfiguratsii glikozidnogo tsentra i prirody aglikona na biologicheskuiu aktivnost'.

Hexyl, octyl, and cyclohexyl beta-glycosides and heptyl and cyclohexyl alpha-glycosides of muramyl dipeptide (MDP) were synthesized. Tests in vitro and in vivo revealed lower immunostimulating activities of MDP alpha-glycosides in comparison with the corresponding beta-glycosides and MDP itself. In the case of alkyl beta-glycosides, differences in hydrocarbon chain lengths (C4-C8) and in aglycone (aliphatic chain and aliphatic or aromatic ring) exerted no substantial effect on the immunostimulating activity.

[Synthesis of N-acetylglucosamine beta-aryl glycosides catalyzed by crown ethers]. / Kataliziruemyi kraun-soedineniiami sintez beta-arilglikozidov N-atsetilgliukozamina.

Glycosylation of phenols of various structure with alpha-D-glucosaminyl chloride peracetate in a solid phase-liquid system catalyzed by crown compounds was studied. The highest yields of aryl beta-glycosides were observed at room temperature in acetonitrile using anhydrous potassium carbonate as a base. The optimum phenol-glycosyl donor-base-crown ether ratio was 1:1:1:0.2.

[Synthesis of N-acetylmuramoyl-L-alanyl-D-isoglutamine beta-aryl glycosides]. / Sintez beta-arilglikozidov N-atsetilmuramoil-L-alanil-D-izoglutamina.

Synthesis of N-acetylmuramyl-L-alanyl-D-isoglutamine phenyl and naphthyl-2 beta-glycosides, novel muramyl dipeptide derivatives with phenolic aglycones, was reported. The starting N-glucosamine aryl glycosides were obtained by glycosylation of phenols with peracetylated alpha-glucosaminyl chloride under the conditions of phase-transfer catalysis and used for the synthesis of 4,6-O-isopropylidene-N-acetylmyramic acid aryl beta-glycosides. Condensation of these derivatives with a dipeptide and subsequent deprotection resulted in the target glycopeptides.

[Effect of saponins from Hedera taurica Carr. and modified muramylpeptides on replication of human immunodeficiency virus in vitro]. / Vliianie saponinov iz Hedera taurica Carr. i modifitsirovannykh muramilpeptidov na reproduktsiiu virusa immunodefitsita cheloveka in vitro.

The effects of muramyldipeptide (MDP), several new MDP derivatives, and saponins derived from Hedera taurica Carr, on the in vitro replication of HIV-1 were studied. The coefficient of alteration of the rate of HIV replication was used to compare these reagents' effects on virus replication in Jurkat-tat cells. This coefficient was calculated as the ratio of concentrations of HIV p24 in supernatants to the amount of viable cells. Muramylpeptides boosted HIV replication. Only one modified muramylpeptide alpha-butyl-MDP and tauroside H2 were not capable of boosting HIV-1 antigen production.

[Synthesis of lipophilic muramoyldipeptide derivatives]. / Sintez lipofil'nykh proizvodnykh muramoildipeptida.

beta-Glycosides of N-acetylglucosamine, obtained by the oxazoline synthesis, with 2-dodecyltetradecanol-1 and 2,3-didodecyloxypropanol-1 as aglycons, were converted into muramic acids and then coupled with the dipeptide to give lipophilic glycosides of muramoyldipeptide. On the other hand, condensation of 2-dodecyltetradecanyl esters of glycine and 6-aminohexanoic acid with Boc-L-Ala-D-Glu-NH2 gave the corresponding lipophilic tripeptides, which upon coupling with alpha-benzyl-4,6-O-benzylyden-N-acetylmuramic acid yielded lipophilic esters of muramoyltripeptides. The protecting groups were removed by acid hydrolysis and hydrogenolysis.