Volume 53, Nº 2 (2017)

Synthesis was performed of individual methyl [(S,2R,3S)-4-nitro-1-oxo-1,3-diphenylbutan-2-yl]-(phenyl)phosphinate from racemic β-keto phosphinate and ω-nitrostyrene under the catalysis by nickel(II) complex with (1R,2R)-N,N'-dibenzylcyclohexane-1,2-diamine.

Adamantylation of esters of dicarboxylic acids with 1,3-dehydroadamantane under mild conditions afforded in high yields diesters of (adamantan-1-yl)-substituted unsymmetrical dicarboxylic acids.

Reactions of arylacetic acids with N-methoxymethanamine afford corresponding Weinreb amides which at alkenylation with methallyl and prenyl bromides in the presence of (Me₃Si)₂N^–Na⁺ form unsaturated amides ArCHRCONMe(OMe) (R = CH₂CMe=CH₂, CH₂C=CMe₂). Amides readily react with BuLi and BnMgCl to give ketones ArCHRCOR' (R' = Bu, Bn). A stereoselective reduction of the latter with LiBH(s-Bu)₃ leads to a quantitative formation of syn-isomers of 2-aryl-4-en-1-ols.

Aminomethylation of 2-methyl(aryl)-, 2-aryl-3-alkylpyrroles, 4,5,6,7-tetrahydroindole and its 1-vinyl- and 1-benzyl-substituted derivatives with a mixture of 5% water-ethanol solution of formaldehyde and cyclic amine (pyrrolidine, piperazine, and morpholine) without catalyst at room temperature leads to the formation of the corresponding 2-aminomethylpyrroles and 2-aminomethyl-4,5,6,7-tetrahydroindoles in up to 92% yields. In reaction of 1-vinyl-4,5,6,7-tetrahydroindole with formaldehyde water solution and piperazine in a 60% yield 1,4-bis(1-vinyl-4,5,6,7-tetrahydroindol-2-yl)piperazine was obtained, a promising bifunctional monomer and a building block for the synthesis of new indole derivatives, in particular, of biologically active polymers. In the reaction of 2-methylpyrrole and 4,5,6,7-tetrahydroindole with formaldehyde and morpholine along with the С²-aminomethylation the 1-hydroxymethylation of the pyrrole ring was observed.

Acid-catalyzed reaction of 1-[(4-chlorophenyl)sulfonyl]-2-ethoxypyrrolidine with phenols leads to the formation of new 1-(arylsulfonyl)pyrrolidines. The reaction proceeds under mild conditions and may be used as a convenient method for the synthesis of pyrrolidine-1-sulfonylarene derivatives containing a phenol fragment in the position 2.

Convenient method of one-pot tricomponent synthesis of (arylamino)methylidene-3?-furan-2-ones was developed. Basing on combined spectral data and NOE-experiments the features of stereostructures of obtained arylaminomethylidenederivatives were revealed.

Liquid-phase catalytic reduction of 1,2,3-substituted 5,6,7,8-tetrahydroisoquinolinium perchlorates was investigated. The reaction proceeds stereodirectionally affording cis-decahydroisoquinolines. The probable scheme of reaction products formation is suggested. The structure of compounds obtained was established by IR and ¹³C NMR spectroscopy.

Reactions of diazomethane with quinone mono(di)imines and methylidene quinone imines of pyrido[1,2-a]benzimidazole series occurs by the route of 1,3-dipolar cycloaddition and leads to the formation of quinoid compounds, in particular, previously unknown heterocyclic structures of indazolo[7',6':4,5]imidazo-[2,1-j]quinoline, indazolo[7',6':4,5]imidazo[2,1-e]acridine, indazolo[4',5':4,5]imidazo[2,1-j]quinoline, and indazolo[4',5':4,5]imidazo[2,1-e]acridine.

Condensation of acetylferrocene with 5-phenyl(4-methylphenyl)-1,2-oxazole-3-carbaldehydes afforded (Е)-3-[5-phenyl(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-ones. Reactions of (Е)-3-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-one with semicarbazide, thiosemicarbazide, and hydroxylamine led to the formation of 5-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-3-ferrocenyl-4,5-dihydro-1H-pyrazole- 1-carboxamide, 5-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-3-ferrocenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide, and 5-(4-methylphenyl)-3'-ferrocenyl-4',5'-dihydro-3,5'-bi-1,2-oxazole respectively. Reactions of (Е)-3-[5-(4-methylphenyl)-1,2-oxazol-3-yl]-1-ferrocenylprop-2-en-1-one with guanidine and thiourea result in 4-[5-(4-methyl-phenyl)-1,2-oxazol-3-yl]-6-ferrocenylpyrimidin-2-amine and -2-thione respectively.

New amides of 2-(arylamino)pyrimidine series were synthesized with pharmacophoric fragments of tyrosine kinase and histone deacetylase inhibitors and functional groups providing chemosorption of compounds on nanocarriers.

New synthetic opportunities of conjugated and saturated β-aminoketones were revealed consisting in heterocyclization reactions with the formation of spirochromenes and hydropyrimidinethiones. Alicyclic conjugated Mannich bases under conditions of basic catalysis suffer deamination followed by [4+2]-cycloaddition leading to the stereo- and regiodirected formation of difficultly available spirochromene derivatives. Three-component condensation of acyclic and alicyclic Mannich ketones with thiourea and aromatic aldehydes under aprotic acid catalysis afforded functionalized derivatives of pyrimidine-2-thione series. Optimum conditions were found for О,N-heterocyclization of β-aminocarbonyl substrates.

A method of synthesis of N-carboxyalkyl-substituted dithiaza- and dioxadithiazacycloalkanes was developed consisting in a tricomponent [1+2+1]-cyclocondensation of amino acids with formaldehyde and aliphatic α,ω-dithiols (1,3-propane-, 1,4-butanedithiols, 3,6-dioxa-1,8-octanedithiol).

Reactions of 6-bromo- and 6-iodo-6-deoxy-β-cyclodextrin with organic amines of diverse nature afforded a series of monocationic derivatives with aminium groups located in the cyclodextrin scaffold on the side of the primary hydroxy groups. The structure and composition of the obtained cationic β-cyclodextrin derivatives were confirmed by ¹H and ¹³C NMR data.

Reactions of aromatic and aliphatic nitriles with chloromethyl propargyl ether in the presence of activated zinc followed by treatment with water in the presence of H₃PMo₁₂O₄₀ afforded β-oxoethers.

Reaction of tellurium tetrachloride with 4-octyne occurs as an anti-addition and leads to the formation of trichloro[(Е)-1-propyl-2-chloropent-1-enyl]tellane which was reduced sodium metabisulfite in a two-phase system C₆Н₆–H₂O affording bis[(Е)-1-propyl-2-chloropent-1-enyl]ditellane.

N-Alkylidene-1-(propargylsulfanyl)-2-(1H-pyrrol-1-yl)buta-1,3-dien-1-amines at treatment by a superbasic system t-BuONa–THF–DMSO under standard conditions of the synthesis of seven-membered azaheterocycles are chemo- and stereoselectively converted into 4,4-disubstituted 5-ethenylidene-2-[(Z)-1-(1H-pyrrol-1-yl)prop-1-enyl]-4,5-dihydro-1,3-thiazoles.

Aminomethylation of calix[4]resorcinarenes with (1-hydroxyethane-1,1-diyl)bisphosphonic acid afforded a series of new water soluble onium salts.