A. A. Fatykhov

Disaccharide blocks for analogs of OSW-1

The acetalization of phenyl 1-thio-α-L-arabinopyranoside with 2,3-butanedione in the medium of MeOH-CH(OMe)3-CSA proceeded with the prevailing formation of the corresponding 3,4-bisacetal that further was converted in compounds, which were regio- and stereoisomers of disaccharide block of OSW-1.

Condensation of acetylacetone with formaldehyde and thiols

Acetylacetone reacted with formaldehyde and thiols in aqueous medium or in the presence of 0.1 equiv of sodium hydroxide to give the corresponding 3-[(alkylsulfanyl)methyl]pentane-2,4-diones which exist in solution as mixtures of diketone and enol tautomers. Four-component condensation of acetylacetone with formaldehyde, methanethiol, and sodium sulfide, depending on the reaction time, led to the formation of a mixture of 1,1-bis(methylsulfanylmethyl)propan-2-one with 1,1′-{3-[(methylsulfanyl)methyl]tetrahydro-2H-thiopyran-3,5-diyl}diethanone or with 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one.

Preparation of methano[1,3]oxazolo[3,2-a]quinolin-2-ones from 2-(pent-3-en-2-yl)anilines

Acid-catalyzed Claisen aromatic rearrangement of ethyl N-(pent-3-en-2-yl)-N-phenylglycinate leads to the formation of ethyl N-[2-(pent-3-en-2-yl)phenyl]glycinate. The reaction of sodium salt of N-acetyl-2-(pent-3-en-2-yl)-4-methylaniline with methyl bromoacetate afforded ethyl N-acetyl-N-[4-methyl-2-(pent-3-en-2-yl)phenyl]glycinate. The hydrolysis of synthesized esters, the conversion of the obtained acids by treating with ethyl chloroformate into munchnones, and the subsequent [3+2]-cycloaddition provided methoxazoloquinoline structures.

Synthesis of 1-{4a,6-dimethyl-4a,9a-dihydropyrano-[3,4-b]indol-9(1H)-yl}ethanone

Heating of the bromination product of 4-methyl-3,6-dihydro-2H-pyran with 4-toluidine or 2-bromo-4-methylamiline in triethylamine gave 4-methyl-N-(4-methylphenyl)- and N-(2-bromo-4-methylphenyl)-4-methyl-3,6-dihydro-2H-pyran-3-amines which were converted into the corresponding amides by reaction with bromo- or chloroacetyl chloride. 1-{4a,6-Dimethyl-4a,9a-dihydropyrano[3,4-b]indol-9(1H)-yl} ethanone was synthesized in good yield by heating N-(2-bromo-4-methylphenyl)-N-(4-methyl-3,6-dihydro-2Hpyran-3-yl)acetamide in boiling toluene in the presence of palladium(II) acetate, triphenylphosphine, copper(II) acetate, triethylamine, and potassium carbonate.

Synthesis of N-acetyl-3,3a,4,8b- and -1,3a,4,8b-tetrahydrocyclopenta[b]indoles from N- and 2-(cyclopent-2-en-1-yl)anilines

Reactions of 2-bromo-N-(cyclopent-2-en-1-yl)-4-methylaniline and N-(cyclopent-2-en-1-yl)-2-iodo-4,6-dimethylaniline with acetyl bromide in the presence of potassium carbonate gave mixtures of syn and anti atropisomers of the corresponding N-acetyl derivatives at ratios of 1: 1 and 3: 2 respectively. Heating of these mixtures in toluene in the presence of Pd(OAc)2, PPh3, Et3N, and K2CO3 (KOAc) afforded mixtures of isomeric N-acetyl-7-methyl-3,3a,4,8b- and -1,3a,4,8b-tetrahydrocyclopenta[b]indoles at a ratio of 3: 1 or N-acetyl-5,7-dimethyl-3,3a,4,8b- and -1,3a,4,8b-tetrahydrocyclopenta[b]indoles at a ratio of 2: 3. N-Acetyl-3,3a,4,8b-tetrahydrocyclopenta[b]indole was found to undergo thermal isomerization into N-acetyl-1,3a,4,8btetrahydrocyclopenta[b]indole.

Bis(Allyloxycarbonyl)methano derivatives of fullerene C60

Mono-, bis-, tris-, tetrakis-, and hexakis-substituted cyclopropanation products of fullerene C60 with diallyl malonate were synthesized according to Bingel-Hirsch. Except for the monocyclopropanation product, all other adducts were isolated as mixtures of regioisomers.

Synthesis of oxo derivatives of N-(p-tolysulfonyl)hexahydrocycloalka[b]indoles

Hydroxymercuration-demercuration of N-p-tolysulfonyl-4,4a,9,9a-tetrahydro-3H-carbazoles and N-p-tolyl(or methyl)sulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles leads to the formation of the corresponding N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-2-ols and N-p-tolyl(or methyl)sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-2-ols. The latter are oxidized to 2-oxo derivatives with potassium dichromate. The oxidation of 2-methoxy-8-methyl-N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-ol under analogous conditions gives 2-methoxy-8-methyl-N-p-tolysulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-one.

Synthesis of New Pyrazole–Methylmaleopimarate Conjugates

Regiospecific synthesis of conjugates containing a diterpenoid fragment and a pyrazole-ring pharmacophore by 1,3-dipolar cycloaddition of diazomethane to allenoates in the presence of Et3N was demonstrated.

Synthesis of (5R*)- and (5S*)-5,7,11-trimethyl-3a-phenyl-4,5-dihydro-3aH-1,4-methano[1,3]oxazolo[3,2-a]quinolin-2-ones

Heating of N-benzoyl-N-[2-(1-methylbut-2-en-1-yl)-4-methylphenyl]glycine with ethyl chloroformate or acetic anhydride gave (5R*) and (5S*) isomers of (1R*,3aS*,4S*,11S*)-5,7,11-trimethyl-3a-phenyl-4,5-dihydro-3aH-1,4-methano[1,3]oxazolo[3,2-a]quinolin-2-one.

Thermal oligomerization of methyl 4-(1,3-dioxo-2,3-dihydro-1H-isoindol-2-yl)buta-2,3-dienoate

Dimeric compounds formed as a result of thermal oligomerization of methyl 4-(1,3-dioxo-2,3- dihydro-1H-isoindol-2-yl)buta-2,3-dienoate were identified.