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A chemoselective synthesis of acyclic and cyclic S-containing aminobenzamides was developed. The method involved samarium-catalyzed thiomethylation of regioisomeric aminobenzamides at the amino group using either bis(N,N-dimethylamino)methane and α,ω-alkanedithiols or bis-1,3-aminosulfides.

An efficient method for the catalytic thiomethylation of regioisomeric aminobenzamides with bis(N,N-dimethylamino)methane (formaldehyde) and H2S (Na2S · 9H2O, NaHS) leading to acyclic S-containing aminobenzamide derivatives or N,S-heterocycles has been developed.

The main route of a new reaction of (dichloromethyl)arenes with S-methyl diethylthiophosphinate is the attack of the thiol sulfur atom (P–SMe) on the methylene carbon atom. A new method for synthesizing dimethyl dithioacetals of arenecarbaldehydes without using highly toxic methanethiol was developed. The suggested approach involves di(dechloromethylthioylation) of the dichloromethyl group of (dichloromethyl)arenes with S-methyl diethylthiophosphinate at a reagent ratio of 1: 2.

An ef cient synthesis of diazaalkatetraynes and tetraaza macroheterocycles by the Mannich aminomethylation of α,ω-di(tetra)acetylenes with secondary diamines and aldehydes using CuCl as a catalyst was developed.

The literature data on the synthesis and properties of oxo-functionalized acyclic and cyclic sulfides obtained by the catalytic multicomponent reactions of 1,3-dicarbonyl compounds with formaldehyde and S-nucleophiles are summarized. An approach to the multimolecular four-component heterocyclization of 1,3-dicarbonyl compounds with CH2O and S- and N-nucleophiles in the synthesis of sulfanyl-substituted azaheterocycles is discussed.

Thiomethylation of carboxylic acid hydrazides with dimethylaminomethyl sulfides RSCH2NMe2 yielded the corresponding N′,N′-bis(sulfanylmethyl)carbohydrazides. When bis-sulfides Me2NCH2S(CH2)nSCH2NMe2 (n = 2–4) are used for thiomethylation, N-(acylamino)-substituted 1,5-dithia-3-azacycloalkanes are formed. These compounds can also be synthesized by CuCl2·2H2O-catalyzed thiomethylation of carboxylic acid hydrazides with either CH2O and thiols or α,ω-alkanedithiols.

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.

An efficient method for the synthesis of spiro[3.3]heptanes and spiro[3.4]octanes of various structures has been developed using cycloalumination of substituted methylidenecyclobutanes with Et3Al in the presence of Cp2ZrCl2. A possibility of transformation of the in situ formed spiroaluminacyclopentanes to the corresponding thiophanes, selenophanes, and cyclopentanols in high yields and selectivity has been demonstrated.

Catalytic cycloalumination of cyclonona-1,2-diene upon treatment with Et3Al and EtAlCl2 in the presence of Cp2ZrCl2, leading to 10-ethyl-10-aluminabicyclo[7.3.01,9]dodec-8-ene (1) and 11-ethyl-11-aluminatricyclo[10.7.01,12.02,10]nonadeca-9,12-diene, respectively, was accomplished in high yields. A possibility for the selective transformation of compound 1 to 1-allyl-9-(pent-4-enyl)cyclonon-1-ene and 10-hydroxybicyclo[7.3.01,9]dodec-8-ene in one preparative step was demonstrated.

Cyclopentanols were synthesized by a “one-pot” method involving Cp2ZrCl2-catalyzed cycloalumination of α-olefins with trialkylalanes followed by the in situ reactions of aluminacyclopentanes with esters in the presence of catalytic amounts of Cu, Ni or Pd salts and complexes.

Cobalt-containing complexes capable of catalyzing reactions of trialkyl- and alkylhaloalanes (RnAlCl3–n) with olefins, allenes, and acetylenes were synthesized. The reactions afford cyclic and acyclic organoaluminum compounds.

A method for the synthesis of secondary and tertiary alcohols was developed. The method is based on cycloalumination of olefins with trialkylalanes in the presence of Zr-containing catalysts followed by the CuCl-catalyzed in situ reaction of the corresponding aluminacyclopentanes with aldehydes or ketones.

Catalytic methods were developed for the synthesis of acyclic 1,2- and 1,4-dialuminum compounds by the reactions of olefins, dienes, or acetylenes with R2AlCl (R = Et, Et2N, (cyclo-C6H11)2N, BunO, or n-C6H13O) in the presence of Ti- or Zr-containing complex catalysts and magnesium metal as an acceptor of chloride ions.

Catalytic cycloalumination of allenes with EtAlCl2 in the presence of Ti or Zr complexes afforded methylidene- and alkyl(benzyl)idenealuminacyclopropanes and the corresponding aluminacyclopentanes, which were identified by analyzing the hydrolysis products. The reactions with the use of Et2AlCl instead of EtAlCl2 produced 1,2- and 1,4-dialuminum compounds.