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An efficient method for the synthesis of N-aryltetraoxazaspiroalkanes by ring transformation of pentaoxaspiroalkanes with arylamines catalyzed by Sm(NO3)3·6H2O has been developed.

A catalytic method for the selective synthesis of novel bis(1,3-diketone-2-ylmethylsulfanyl)alkanes via the thiomethylation reactions of aliphatic 1,3-diketones with СН2О and α,ω-dithiols is provided. Selective cyclothiomethylation of 1-phenylbutane-1,3-dione has been realized using a tandem catalyst Cp2Zr(Ti)Cl2-BuONa to form 6-benzoyl-1,4-dithiepane. Proposed mechanisms of catalytic thiomethylation reactions are also discussed.

An effective method for the synthesis of otherwise hardly accessible title triazine derivatives (IV) via a Sm-catalyzed multicomponent reaction is developed.

A selective method for the synthesis of 3-(alk-2-yn-1-yl)-1,3-oxazolidines has been developed by the reaction of bis(oxazolidin-3-yl)methanes with terminal acetylenes with copper-containing catalysts. The reaction of terminal acetylenes with optically active bis((4R)-4-ethyl-1,3-oxazolidin-yl)methane led to the formation of (4R)-3-(2-alkynyl)-4-ethyl-1,3-oxazolidines.

Two alternative methods for the synthesis of novel N-hydroxyalkyldithiazepanes (III) by recyclization of 1-oxa-3,6-dithiacycloheptane (I) with amino alcohols (II) or intermolecular cyclization of 1,2-ethanedithiol with methoxymethylamino alcohols (V) are developed.

Multicomponent reaction of acetylacetone with formaldehyde and S-nucleophiles followed by in situ reaction of bisdiketone intermediates formed [cf.

A facile protocol allows the intermolecular three-component cyclocondensation of dithiols, formaldehyde, and amines to give 1,3,5-dithiazepanes and a wide variety of macroheterocycles.

A new method was developed for preparation of N-(1,5,3-dithiazepan-5-yl)- and N-(1,5,3-dithiazocan-5-yl)amides by transamination of N-tert-butyl-1,5,3-dithiazepane and N-tert-butyl-1,5,3-dithiazocane, and also by recyclization of 1-oxa-3,6-dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane with carboxylic acids hydrazides in the presence of catalysts based on rare earth elements.

Efficient methods for the synthesis of α,ω-bis-1,5,3-dithiazepanes based on the heterocyclization of α,ω-diamines with N 1,N 1,N 6,N 6-tetramethyl-2,5-dithiahexane-1,6-diamine and on the intermolecular cyclization of 1,2-ethanedithiol with tetrakis(methoxymethyl)diamines catalyzed by SmCl3∙6H2O have been developed.

An efficient one-pot procedure has been developed for the synthesis of bis-1,5,3-dithiazepanes by reaction of ethane-1,2-dithiol with formaldehyde and ammonium salts. According to the X-ray diffraction data, the heterorings in 3,3′-[ethane-1,2-diylbis(sulfanediylmethanediyl)]bis(1,5,3-dithiazepane) in crystal adopt a chair conformation with axial orientation of the substituent on the nitrogen atom.

N′,N′-bis(sulfanylmethyl)carbohydrazides and N-substituted dithiazepanes, dithiazocanes, and dithiazonanes are efficiently obtained by thiomethylation of carboxylic acid hydrazides mediated by transition metal-based and rare earth-based catalysts.

Efficient procedures have been developed for the synthesis of 5-alkyl-1,3,5-triazinan-2-ones and 5-alkyl-1,3,5-triazinane-2-thiones by reaction of urea (thiourea) with primary alkylamines and N,N,N′,N′-tetramethylmethylenediamine and by reaction of primary amines with N,N′-bis(dimethylaminomethyl)urea(thiourea) in the presence of Cu- and Sm-containing catalysts.

Additionally 3-hetaryl-1,5,3-dithiazepanes are synthesized in comparable yields to 3-hetaryl-1,5,3-dithiazocanes (IV).

Efficient preparation method was developed for N-aryl(benzyl, alkyl)-1,5,3-dithiazocan-3-amines consisting in the transamination of 3-tert-butyl-1,5,3-dithiazocane with aryl(benzyl)hydrazines, and also in the reaction of N1,N1,N7,N7-tetramethyl-2,6-dithiaheptane-1,7-diamine with aryl(benzyl, alkyl)hydrazines in the presence of catalytic amounts of Ti and Cu compounds.

Selective methods were developed for the synthesis of N-aryl-1,5,3-dithiazepinanes and N-aryl-1,5,3-dithiazocinanes by transamination of N-tert-butyl-1,5,3-dithiazepinane or recyclization of 1-oxa-3,6-dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane by the action of aniline derivatives in the presence of Sm(NO3)3·6H2O catalyst.

Efficient procedures for the synthesis of the title compounds (IV) are developed using cyclocondensation as well as by transamination processes.

Applying tetramethylmethanediamine (I) in a new approach to aminomethylation of mono- and dithiols (II) and (IV) in the presence of samarium and iron salts affords the aminosulfides (III) and diaminodisulfides (V) with high yields and selectivity.

An efficient synthetic procedure was developed for preparation of oxygen-containing propargylamines with high yields and selectivity by aminomethylation of propargyl alcohols and their esters with gem-diamines catalyzed by complexes and salts of d-transition metals and lanthanides.

A catalytic method for the efficient synthesis of 5,6-open and 6,6-closed (2π+1π) fullerene adducts by [2+1] cycloaddition of ethyl 2-alkyl(hetaryl)-2-diazoacetates to [60]fullerene in the presence of a three-component catalyst Pd(acac)2—PPh3—Et3Al have been developed.

Zirconocene-catalyzed reaction of polycyclic methylenecyclobutane derivatives, e.g. (I), with Et3Al generates 5-membered cycloaluminates like (III) which can be quenched by reaction with sulfur, selenium, allyl chloride or methyl formate to give spirocyclic derivatives, e.g. (IV), (VI), (VII).

A novel method for the synthesis of 2-vinylalkanes by reaction of 3-alkyl-substituted aluminacyclopentanes with functionalized allyl compounds in the presence of catalytic amounts of Ni or Co complexes is proposed.

Substituted quinolines are synthesized in an effective one-step procedure via reaction of o-iodoaniline with alk-2-yn-1-amines.