R. I. Khusnutdinov

Hydroamination of conjugated dienes catalyzed by transition metal complexes

The review summarizes published data on the hydroamination of 1,3-dienes with various primary and secondary amines, ammonia, and ammonium salts of mineral acids in the presence of transition metal complexes under homogeneous conditions. The effects of the nature of metal, ligand, initial diene, and amine and reaction conditions on the selectivity of hydroamination are considered, and possible reaction mechanisms are discussed.

Furfuryl Alcohol in Synthesis of Levulinic Acid Esters and Difurylmethane with Fe and Rh Complexes

The possibility of synthesis of levulinic acid esters by the reaction of furfuryl alcohol with aliphatic alcohols in the system CCl4-Fe(acac)3 was studied.

Manganese compounds in the catalysis of organic reactions

The review summarizes published data on the use of manganese compounds as catalysts in oxidation of alkanes, alcohols, aldehydes, sulfides, and amines and carbometalation, cross coupling, telomerization, chlorination, hydrosilylation, hydrohydrazination, and other reactions.

Generation of alkyl hypochlorites in oxidation of alcohols with carbon tetrachloride catalyzed by vanadium and manganese compounds

Primary alcohols and diols with various structures were subjected to transformations into esters, aldehydes, ketones, and lactones under the action of carbon tetrachloride in the presence of manganese compounds (MnCl2, MnO2, Mn(OAc)2, Mn(acac)3) and vanadium compounds (VCl5, V2O5, VO(acac)2) as catalysts. These transformation proceeded with the involvement of alkyl hypochlorites, which were generated in the course of oxidation of alcohols with carbon tetrachloride catalyzed by manganese or vanadium compounds. The optimum molar ratios between the catalyst and reagents were determined, and the reaction conditions for the highly selective synthesis of esters, aldehydes, ketones, and lactones from alcohols were found.

Synthesis of alkyl methyl ethers and alkyl methyl carbonates by reaction of alcohols with dimethyl carbonate in the presence of tungsten and cobalt complexes

Alkyl methyl ethers and alkyl methyl carbonates were synthesized by reaction of alcohols with dimethyl carbonate in the presence of tungsten and cobalt carbonyls. Optimal reactant and catalyst ratios, as well as reaction conditions, were found for selective formation of alkyl methyl ethers or alkyl methyl carbonates.

Synthesis of N-alkylanilines and substituted quinolines by reaction of aniline with alcohols and CCl4 effected with Ni-containing catalysts

Syntheses of N-alkylanilines and 2,3-disubstituted quinolines by the reaction of aniline with CCl4 and aliphatic alcohols under the action of nickel-containing catalysts, in particular, Ni(OAc)2·4H2O-Et3N.

Electrochemical studies of nickel complexes containing phoshprus(III) ligands and their related Ziegler catalysts

Abstract All of the data obtained by electrochemical methods involving the mercury electrode, spectrophotometry and conductometry have showed the stepwise formations of a neutral σ-donor-acceptor pentacoordinated NiX2-L3 and a cationic tetracoordinated NiL42+, associated with a shift in the dissociation-coordination equilibrium owing to an excessive concentration of the ligand in solutions of the binary systems containing NiII compounds coordinated with acid ligands (X = Cl−, No3−, acac) and the trivalent phosphorus ligands (L = Pbu3, PPh3, P(OEt)3, P(O-i-Pr)3, P(O-s-Bu)3, P(OC6H11), P(OPh3). The complexes have for the first time been prepared for all the phosphines and phosphites studied. Ni(acac)2 was found to enhance coordination by the phosphines and phosphites in acetonitrile. The value of the semiwave potential shift (ΔE 1 2 , V) towards less negative potentials depends on the number of ligands present in the inner coordination sphere of metal, and was found to be 200–300 and 800–1300 mV for NiX2L2 and NiL42+, respectively. The electrochemical reduction of NiL42+ complexes into the zero-valent nickel isostructural complexes is reversible with values similar to that of the nickel formal potential Ni2+/Ni0 (E 1 2 = E0 = −0.25 V). For the first time, the homogeneous formations of catalytically active complexes have been studied electrochemically in situ with the tricomponent Ziegler-Natta catalytic systems to give stable NiII complexes in toluene solutions of Ni(acac)2-{PR3 or P(OR)3}-OAC (Ni/P/Al = 1/4/4/) at T ⩽ −10°C. These complexes can undergo reversible reductions and determine catalytic activity of the system. They are regarded as ionic and are tentatively assigned the structure of bimetallic complexes [RNiL3]+[AIR4]−. The hydride complexes of divalent nickel HNiL4+ were found to be as catalytically active as the Ni(acac)2-P(OR)3{R = Et, i-Pr}-AlEt3 (Ni/P/Al = 1/4/4) systems formed in toluene-isopropanol solvent at T = −10 to +25°C. The activating affect by the organic phosphorus ligand on the electronic state of Ni has been found for the first time to decrease the energy levels of the boundary orbitals as the coordination sphere becomes saturated with the ligand, thus changing the ligands environment and configuration of the complex, the degree of alkylation and the degree of stabilization of the catalytically active complexes. In the case of the NiL42+ complexes, the ligand-to-metal charge transfer energies permitted the estimation of the affinity to the nickel electron inherent to the nickel LUMO energy level in the given complex, that energy being similar to HOMO energy in Ni0L4 under the conditions of the reversible electronic process.

Synthesis of N-benzylidenebenzylamine from benzylamine under the action of iron-containing catalysts in CCl4

A direct synthesis of N-benzylidenebenzylamine from benzylamine in the presence of iron-containing catalysts was performed with the 92–96% yield. The reaction proceeds in tetrachloromethane at 80–85°C over 8 h.

Synthesis of substituted quinolines by the reaction of anilines with alcohols and CCl4 in the presence of Fe-containing catalysts

Substituted quinolines were synthesized by the reaction of aniline derivatives with aliphatic alcohols and CCl4 upon the action of the FeCl3·6H2O catalyst.

Intermolecular dehydration of alcohols by the action of copper compounds activated with carbon tetrabromide. Synthesis of ethers

Copper compounds of the general formula CuXn (X = Cl, Br, I, acac, OAc, C7H4O3, C7H5O2; n = 1, 2) activated by carbon tetrabromide catalyzed intermolecular dehydration of primary and secondary alcohols with formation of the corresponding ethers.