Sergey V. Gorbunov

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 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.

Stereoselective one-pot synthesis of polycyanosubstituted piperidines

An effective and facile multicomponent method for the synthesis of polysubstituted piperidines is described. The Michael–Mannich type cascade of benzylidenemalononitriles with aromatic aldehydes and ammonium acetate or aqueous ammonia provides convenient access to the stereoselective synthesis of 3,3,5,5-tetracyano-2,4,6-triarylpiperidines in good to excellent yields in one-pot manner. Ammonium acetate or aqueous ammonia plays a role both as a catalyst and as a nitrogen source. It is established that the reaction proceeds via sequence of equilibriums and a competitive mechanisms are implemented.Graphical abstract