T. V. Tyumkina

Synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl-1,5,3-dithiazocanes in the presence of samarium- and cobalt-containing catalysts

Efficient procedures were developed for the synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl-1,5,3-dithiazocanes by cyclocondensation of anilines with formaldehyde and α,ω-dithiols (etane-1,2-dithiol and propane-1,3-dithiol), as well as by transamination of N-tert-butyl-1,5,3-dithiazepane or N-tert-butyl-1,5,3-dithiazocane with aromatic amines in the presence of samarium and cobalt complexes.

Multicomponent condensation of aliphatic amines with formaldehyde and hydrogen sulfide

Cyclothiomethylation of primary aliphatic amines with the reagent H2S-CH2O (2:3) in aqueous medium mainly gave substituted dithiazines; oxathiazines and dioxazines were obtained from butylamine and ethanolamine. Under the chosen reaction conditions, ethylenediamine was converted into 5-[2-(perhydro-1,3,5-dithiazin-5-yl)ethyl]perhydro-1,3,5-dithiazine or substituted thiazetidine and oxazetidine, depending on the order of mixing of the starting reagents.

Novel 1,5,3-dithiazepanes: three-component synthesis, stereochemistry, and fungicidal activity

Three-component heterocyclization of hydrazine with formaldehyde and ethane-1,2-dithiol gave previously unknown 3,3′-bi(1,5,3-dithiazepane). Its stereochemistry was determined by X-ray diffraction. The reaction with higher aliphatic aldehydes RCHO (R = Me, Et, Prn, and Bun) yielded 2,4-dialkyl-3-alkylideneamino-1,5,3-dithiazepanes. The stereochemistry of the latter was determined by 1H and 13C NMR spectroscopy and confirmed by quantum chemical calculations. Heterocyclizations of phenylhydrazine and benzylhydrazine with ethane-1,2-dithiol gave 3-amino-1,5,3-dithiazepanes only with CH2O and MeCHO as the aldehyde component. 3,3′-Bi(1,5,3-dithiazepane) and its N-adduct with MeI were found to exhibit fungicidal activity against microscopic fungi.

Synthesis and transformations of metallacycles 40. Catalytic cycloalumination in the synthesis of 3-substituted phospholanes

An efficient one-pot method was developed for the synthesis of 3-alkyland 3-benzyl-substituted phospholanes through the successive Cp2ZrCl2-catalyzed cycloalumination of α-olefins in the presence of AlEt3 giving the corresponding aluminacyclopentanes followed by the in situ replacement of the aluminum atom in the latter compounds by a P atom by means of methyl(phenyl)dichlorophosphines. The oxidation of 3-alkyl- and 3-benzyl-1-methyl(phenyl)-phospholanes with hydrogen peroxide affords 3-alkyl- and 3-benzyl-1-methyl(phenyl)-phospholane 1-oxides, respectively.

Thiomethylation of amino alcohols using formaldehyde and hydrogen sulfide

Three-component condensations of formaldehyde with hydrogen sulfide and hydroxylamine or amino alcohols at a ratio of 3:2:1 give 47–73% of N-hydroxy(or hydroxyalkyl)-1,3,5-dithiazinanes. The reactions of CH2O with H2S and hydroxylamine or α-amino alcohols at a ratio of 4:3:1 involve both amino and hydroxy groups, leading to the corresponding dithiazinanes. 4-Aminobutan-1-ol reacts with CH2O and H2S under analogous conditions only at the amino group to form 4-(1,3,5-dithiazinan-5-yl)butan-1-ol.

First example of one-pot synthesis of hydrocarbon macrorings

Cyclomagnesation of α,ω-diallenes by EtMgBr in the presence of chemically activated Mg and Cp2TiCl2 catalyst led to the formation of cyclic organomagnesium compounds whose hydrolysis provided gigantic hydrocarbon macrorings with 1,5-cis-disubstituted double bonds.

One-pot synthesis of borolanes by reaction of aluminacyclopentanes with BF3·Et2O

A selective procedure was developed for the synthesis of substituted borolanes via transmetalation with BF3 · Et2O of 3-alkyl-1-ethylaluminacyclopentanes obtained from the corresponding terminal olefins and AlEt3 in the presence of Cp2ZrCl2 as a catalyst. 3-Substituted 1-fluoroborolanes were isolated and identified as 1: 1 complexes with EtBF2.

Multicomponent heterocyclization of hydrazine, hydrogen sulfide, and formaldehyde

Multicomponent heterocyclization of hydrazine, hydrogen sulfide, and formaldehyde gave previously unknown bi-, tri-, and tetracyclic nitrogen- and sulfur-containing heterocycles. 3,7-Dithia-1,5-diazabicyclo[3.3.0]octane, 4,9-dithia-1,2,6,7-tetraazatricyclo[5.3.1.12,6]dodecane, and 4,9,14-trithia-1,2,6,7,11,12-hexaazatetracyclo[10.3.1.12,6.17,11]octadecane were obtained selectively, depending on the reaction temperature (0–60 °C).

A quantum chemical study of self-association of HAlBu2i and ClAlBu2i

The self-association of di-iso-butylaluminum hydride and di-iso-butylaluminum chloride is studied at the level of density functional theory and second order Möller-Plesset perturbation theory. Thermodynamic parameters of the monomeric, dimeric, trimeric, and tetrameric forms of HAlBu2i and ClAlBu2i in a range of 203 K to 373 K are calculated. The energy of solvation is taken into account by the COSMO polarized continuum model. Based on the obtained results the equilibrium concentrations of the associated forms of organoaluminum compounds (OACs) are calculated, which agree with the experimental data. So, at room temperature the dimeric or trimeric forms of OACs are dominant in the gas phase and non-polar solvents; the tetrameric form is present, while the concentration of the monomeric form is negligibly low and decreases with decreasing temperature or diluting.

Synthesis and transformations of metallacycles 43. One-pot synthesis of polycyclic 3-alkyl(phenyl)phospholane 3-oxides

A one-pot method for the synthesis of polycyclic phospholanes and phospholane 3-oxides from norbornenes was developed based on their Cp2ZrCl2-catalyzed cycloalumination. The in situ formed polycyclic aluminacyclopentanes were treated with organic dichlorophosphines (RPCl2, where R = Me, But, Ph) to obtain polycyclic phospholanes. The phospholanes were oxidized with hydrogen peroxide to obtain their 3-oxides in 81–92% yields.