Tatiana A. Zaimovskaya

Electrocatalytic transformation of malononitrile and cycloalkylidenemalononitriles into spirotricyclic and spirotetracyclic compounds containing cyclopropane and pyrroline fragments

Electrolysis of cycloalkylidenemalononitriles and malononitrile in MeOH in an undivided cell in the presence of the NaBr—NaOMe mediator system gives spirotricyclic compounds containing cyclopropane and pyrroline fragments in 50—77% yields. Spirobicyclic and spirotricyclic tetracyanocyclopropanes undergo electrolysis in alcohols to afford spirotricyclic and spirotetracyclic products containing cyclopropane and pyrroline fragments in 50—93% 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.

Stereoselective electrocatalytic transformations of malononitrile and aromatic aldehydes into (1R,5S,6R)*-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.

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 α,α-dihalodialkyl ketones giving rise to methyl esters of α,β-unsaturated carboxylic acids in 70—75% substance yields and 60—70% current yields.

Electrochemical cascade assembling of heterocyclic ketones and two molecules of malononitrile: facile and efficient ‘one-pot’ approach to 6-heterospiro[2.5]octane-1,1,2,2-tetracarbonitrile scaffold

The electrochemically induced reaction of heterocyclic ketones and two equivalents of malononitrile in an undivided cell in alcohols in the presence of sodium bromide as mediator leading to the selective formation of substituted 6-heterospirocyclopropane-1,1,2,2-tetracarbonitriles in 50–75% yields as a result of the complex cascade process has been investigated. This new electrocatalytic cascade process smoothly proceeds with different types of heterocyclic ketones and resulted in ‘one-pot’ formation of 6-heterospirocyclopropane-1,1,2,2-tetracarbonitriles with prominent pharmacological and physiological activity. The application of this electrochemical cascade method to the formation of medicinally relevant substituted 6-heterospiro[2.5]octane-1,1,2,2-tetracarbonitriles is also beneficial from the viewpoint of diversity-oriented large-scale processes.Graphical abstract