Electrochemical co-oxidation of C-H acids and methanol as a new route to functionalized cyclopropanes

Electrolysis of dimethyl malonate or methyl cyanoacetate in methanol in the presence of LiCl in an undivided cell leads to formation of 1,1,2,2-cyclopropanetetracarboxylic derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1835–1836, October, 1994.This work was supported by the International Science Foundation (Grant No MHY 000).     

Stereoselective electrocatalytic cyclization of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acid esters to form 6-substituted (1R,5R,6R)*-4,4-dialkoxy-5-cyano-2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylic acid esters

Electrolysis of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acid esters in alcohols in an undivided cell in the presence of NaBr or NaOAc afforded 6-substituted (1R,5R, 6R)*-4,4-dialkoxy-5-cyano-2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylic acid esters in 80–95% yields. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 102–107, January, 2006.     

Crystal and molecular structure of hexacarbomethoxycyclopropane

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 171–173, May–June, 1989.     

Electrochemical dehydrodimerization of malonate esters with double bond formation

Russian Chemical Bulletin -     

Electrochemical oxidation of malonic esters in acetonitrile in the presence of iodides as mediators

Electrochemical oxidation of malonic esters in acetonitrile in the presence of iodides follows two different pathways depending on the nature of the cation. In the presence of Lil, alkyl 1,1,2,2,3,3-propanetetracarboxylates were obtained in 85–98% yields. In the presence of Nal, Kl, or Bu₄NI, the formation of 1,1,2,2-ethanetetracarboxylates and their subsequent dehydrogenation to ethenetetracarboxylates was the main reaction pathway. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 620–623, March, 1997.     

Electrochemical cyclization of tetramethyl esters of 2-substituted propane-1,1,3,3-tetracarboxylic acids in the presence of salts of hydrohalic acids

The chemical and electrochemical cyclization of tetramethyl esters of 2-substituted propane-1,1,3,3-tetracarboxylic acids in the presence of hydrohalic acid salt mediators were studied. It was found that the chemical variant of the cyclization of the corresponding ,'-dianions of esters of propane-1,1,3,3-tetracarboxylic acids by the action of iodine or bromine is substantially inferior to the electrochemical variant. In the latter case, the esters of substituted cyclopopane-1,1,2,2-tetracarboxylic acids are formed in a 87–98% yield. The tetramethyl ester of 2-isopropylpropane-1,1,3,3-tetracarboxylic acid, which under the electrolysis conditions decomposes according to a Michael retroreaction is an exception.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2783–2789, December, 1990.     

Electrochemical oxidation of tetramethyl esters of α,α,ω,ω-alcaneteracarboxylic acids

Cyclization of esters of butane-1,1,4,4- and pentane-1,1,5,5-tetracarboxylic acids during electrolysis in methanol in the presence of Nal produces, with a yield of 95%, the esters of cyclobutane-1,1,2,2- and cyclopentane-1,1,2,2-tetracarboxylic acids. Under similar conditions, esters of the highest ,,,-alkanetetracarboxylic acids undergo iodation and hydroxymethylation due to electrical oxidation of methanol to formaldehyde. During electrolysis in methanol in the presence of NaOAc, the esters of ,,,-alkanetetracarboxylic acids undergo effective hydroxymethylation, followed by cyclization into substituted five- and six-member lactones, or tetrahydrofurans when structurally possible.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2332–2339, October, 1992.     

Electrochemical cyclization of esters of propane-1,1,3,3-tetracarboxylic acids to give esters of substituted cyclopropane-1,1,2,2-tetracarboxylic acids

Conclusions Esters of substituted propane-1,1,3,3-tetracarboxylic acids cyclize to give high yields of esters of substituted cyclopropane-1,1,2,2-tetracarboxylic acids upon electrochemical oxidation in methanol in the presence of sodium iodide as an electron transfer catalyst.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 228–230, January, 1987.     

Electrocatalytic transformation of malononitrile and cycloalkylidenemalononitriles into spirobicyclic and spirotricyclic compounds containing 1,1,2,2-tetracyanocyclopropane fragment

Electrolysis of malononitrile and cycloalkylidenemalononitriles in EtOH in an undivided cell in the presence of NaBr affords spirobicyclic compounds containing a 1,1,2,2-tetracyanocyclopropane fragment in 50—88% yields.