Yurii V. Gatilov

Reaction of Arylpropargyl Aldehydes with 2,3-Bis-hydroxylamino-2,3-dimethylbutane: Synthesis of 2-(1-Hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones

Abstract Reaction of arylpropargyl aldehydes with 2,3-dihydroxylamino-2,3-dimethylbutane results in the formation of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones in high yields (70–80%). Allowing availability of propargyl aldehydes, this method gives new possibilities for the preparation of 2-(1-hydroxy-4,4,5,5-tetramethylimidazolidin-2-ylidene)-1-arylethanones.

Synthesis of nitrogen-containing heterocyclic compounds using perfluoro-2-methylpent-2-ene and perfluoro-5-azanon-4-ene

Abstract Reactions of perfluoro-2-methylpent-2-ena or perfluoro-5-azanon-4-ene with a range of bidentate nitrogen nucleophiles (urea, acet-, benz-, 4-nitrobenz-amidine hydrochloride, 2-aminopyridine, 2-aminobenzimidazole, guanidine) in the presence of Et 3 N or KOH effectively provided partially fluorinated heterocycles of pyrimidine, 2H-pyrido[1,2-a]pyrimidine and [1,3,5]triazine derivatives. The structure of 2-pentafluoroethyl-3-trifluoromethyl-pyrido[1,2-a]pyrimidin-4-one was further confirmed by the X-ray crystallographic analysis.

Base-catalyzed domino cyclization of acetylenes with ketones to functionalized cyclopentenes.

Acetylene reacts with methylaryl(hetaryl)ketones in the presence of 6.5 mol % KOH in DMSO to give diastereoselectively in single operationally functionalized cyclopentenes. This domino cyclization involving two molecules of acetylene and two molecules of ketone proceeds with the formation of four C-C bonds. The complementary assembly of the cyclopentenes with similar functionalities from acetylenes and 1,5-diketones has been developed.

Reaction of perfluoro-2-methylpent-2-ene and perfluoro-5-azanon-4-ene with aniline and its derivatives

Abstract Reaction of perfluoro-2-methylpent-2-ene ( 1 ) and perfluoro-5-azanon-4-ene ( 2 ) with aniline, 4-fluoroaniline, 4-methoxyaniline and 2,6-dimethylaniline in the presence of Et 3 N provides derivatives of quinoline and quinozaline, whereas reaction of 2 yields diazetine derivatives with 2- and 4-nitroanilines, 2,6-dichloroaniline and pentafluoroaniline. The structure of [2-(1,1,2,2,3,3,3-pentafluoroethyl)-3-trifluoromethyl-quinoline-4-yl]-phenylamine is confirmed by X-ray structural data. The routes of reactions and the 19 F and 13 C NMR spectral data of the products are discussed.

Conformational Flexibility of Fused Tetracenedione Propellers Obtained from One-Pot Reductive Dimerization of Acetylenic Quinones

Reductive dimerization of acetylenic anthraquinones provides synthetic access to flexible nonplanar polyaromatics with a tetracenedione core. In solution, these nonplanar, contorted polycycles exist as equilibrating mixtures of two symmetric conformers. The fused tetracenediones are easily reduced and exhibit rich electrochemical behavior.

Synthesis and transformations of perfluoro-2-methyl-3-azido-2-pentene

Abstract Reactions between perfluoro-2-methyl-2-pentene and NaN 3 in acetonitrile at −20°C provided perfluoro-2-methyl-3-azido-2-pentene stable only to 0°C, which decomposed in CCl 4 at 20°C to give 2,2-bis(trifluoromethyl)-3-pentafluoroethylaziridine or in EtOH at 20°C to 4,4-bis(trifluoromethyl)-5-ethoxy-5-pentafluoroethyl-1,2,3-triazoline, whose structure was confirmed by the X-ray crystallographic analysis. The routes of formation for these products have been discussed.

Unexpected transformation of 1,2-bis(N-methoxy-N-nitrosoamino)cycloalkanes: First synthesis of 4,5-dihydro-1,2,3-triazole 2-oxides

Abstract Thermolysis of 1,2-bis( N -methoxy- N -nitrosoamino)cycloalkanes in organic solvents led to 4,5-dihydro-1,2,3-triazole 2-oxides.

The flavanone pinostrobin in the synthesis of coumarin-chalcone hybrids with a triazole linker

The reaction of flavanone pinostrobin with dibromoalkanes in acetone in the presence of potassium carbonate followed the path of retro-Michael addition – О-alkylation and resulted in the formation of the respective 2-(bromoalkoxy)chalcones. Treatment of the latter with sodium azide gave the respective azides, which were highly active in the Сu-catalyzed 1,3-dipolar cycloaddition reaction. The reaction of these azides with 6-substituted 7-ethynylcoumarins gave coumarin-chalcone hybrids containing a 1,2,3-triazole linker.

Rearrangements of ledene and aromadendrene in superacids

Abstract Acid-catalyzed rearrangements of ledene and aromadendrene were studied for the first time. In superacidic media, conversion into compounds with the natural cubebane skeleton was discovered. A marked difference between the compositions of the conversion products of one and the same olefin in superacids and in ordinary acidic media was observed.

Synthetic Transformations of Sesquiterpene Lactones 10*. Synthesis of 13-Arylguaianolides

The Heck reaction of methylidene lactones of guaiane type, arglabin and ludartin, with aryl halides occurs with the formation of the respective (E)- and (Z)-13-arylidene-substituted derivatives and the respective endocyclic isomer, the ratio of which depends on the nature of methylidenelactone and the reaction conditions. The arylation of ludartin occurred with a lower yield of the target products and was accompanied by the formation of chamazulene. The interaction of grosheimin with aryl halides under Heck reaction led to the exocyclic products with (E)- and (Z)-configuration, with the latter as the major isomers. The structure of two compounds was established by X-ray structural analysis.