Stereoselective electrocatalytic transformation of arylidene- or alkylidenemalononitriles and malonate into alkyl (1R,5R,6R)* 6-substituted 5-cyano-4,4-dialkoxy-2-oxo-3-azabicyclo[3.1.0]hexane-1-carboxylates

Electrolysis of arylidene- or alkylidenemalononitriles and malonate in alcohol in an undivided cell in the presence of sodium halide as mediator results in the stereoselective formation of alkyl (1R,5R,6R)* 6-substituted 5-cyano-4,4-dialkoxy-2-oxo-3-azabicyclo[3.1.0]hexan-1-carboxylates in 50-70% yields.     

Stereoselective electrocatalytic transformation of arylidenemalononitriles and malononitrile into (1R,5S,6R)-6-aryl-2-amino-4,4-dialkoxy-1,5-dicyano-3-azabicyclo[3.1.0]hex-2-enes

Electrolysis of arylidenemalononitriles and malononitrile in alcohols in an undivided cell in the presence of sodium bromide as mediator results in the stereoselective formation of (1R,2S,6R)^*-6-aryl-2-amino-4,4-dialkoxy-1,5-dicyano-3-azabicyclo[3.1.0]hex-2-enes in 60-80% yields.     

Electrochemical transformation of cyanoacetic ester and alkylidenecyanoacetic esters into 3-substituted 1,2-dicyanocyclopropane-1,2-dicarboxylates

Electrolysis of cyanoacetic ester and alkylidenecyanoacetic esters in an undivided cell in the presence of mediators (alkali metal halides) gives rise to 3-substituted, 1,2-dicyanocyclopropane-1,2-dicarboxylates in 60–95% yields. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1165–1168, June, 1998.     

Stereoselective electrocatalytic transformation of malonate and alkylidenecyanoacetates into (E)-3-substituted 2-cyanocyclopropane-1,1,2-tricarboxylates

Electrolysis of malonate and alkylidenecyanoacetates in alcohols in an undivided cell in the presence of NaBr results in stereoselective formation of (E)-3-substituted 2-cyanocyclopropane-1,1,2-tricarboxylates in 75-90% yields.     

Electrocatalytic transformation of dialkyl malonates and arylidene- or alkylidenemalononitriles into dialkyl esters of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acids

Electrolysis of alcoholic solutions of dialkyl malonates and arylidene- or alkylidenemalononitriles in the presence of NaBr in an undivided cell gave dialkyl esters of 3-substituted 2,2-dicyanocyclopropane-1,1-dicarboxylic acids in 60–90% yields. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1547–1552, July, 2005.     

Stereoselective electrocatalytic transformations of malononitrile and aromatic aldehydes into (1<Emphasis Type="Italic">R</Emphasis>,5<Emphasis Type="Italic">S</Emphasis>,6<Emphasis Type="Italic">R</Emphasis>)*-4,4-dialkoxy-2-amino-6-aryl-1,5-dicyano-3-azabicyclo[3.1.0]hex-2-enes

Electrolysis of aromatic aldehydes and malononitrile in alcohols in an undivided cell in the presence of a NaBr-NaOAc mediatory system stereoselectively gave bicyclic compounds containing the cyclopropane and pyrroline fragments in 60 to 70% yields. In the bicyclic products, the benzene and pyrroline rings are on different sides of the cyclopropane ring.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 663–667, March, 2005.     

Electrochemically induced Favorsky rearrangement: transformations of dialkyl ketones into α,β-unsaturated carboxylic esters

Electrolysis of dialkyl ketones in MeOH in the presence of the NaI—NaOH mediator system placed in an undivided cell involves a process analogous to the Favorsky rearrangement of ,-dihalodialkyl ketones giving rise to methyl esters of ,-unsaturated carboxylic acids in 70—75% substance yields and 60—70% current yields.     

A new strategy of the chemical route to the cyclopropane structure: direct transformation of benzylidenemalononitriles and malononitrile into 1,1,2,2-tetracyanocyclopropanes

The new reaction was found: the direct formation of cyclopropanes from activated olefins and C-H acids. The action of free halogen or active halogen containing compounds on the equal amounts of benzylidenemalononitriles and malononitrile in basic alcohol solutions results in the formation of 3-aryl-1,1,2,2-tetracyanocyclopropanes in 65-95% yields. Thus, the new simple and efficient way to 3-aryl substituted tetracyanocyclopropanes was found directly from such simple and reasonable starting compounds as benzylidenemalononitriles and malononitrile.     

Electrochemical conversions of alkyl alkylidenecyanoacetates into 3-substituted dialkyl 1,2-dicyanocyclopropane-1,2-dicarboxylates

Electrolysis of alkyl alkylidenecyanoacetates in an undivided cell in the presence of alkali metal halides as mediators afforded 3-substituted dialkyl 1,2-dicyanocyclopropane-1,2-dicarboxylates in 50–85% yields. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1546–1549, August, 1999.     

Stereoselective electrochemical transformation of 4-substituted cyclohexanones into cis-5-substituted 2,2-dimethoxycyclohexanols

Electrolysis of 4-substituted cyclohexanones in methanol in the presence of sodium halides as mediators in an undivided cell results in the stereoselective formation of cis-5-substituted 2,2-dimethoxycyclohexanols in 70—80% yields.