Electrocatalytic oxidation of N,N'-dialkylbarbituric acids with alkali metal halides as mediators leads to the selective and efficient formation of 2'H-5,5':5',5 ''-terpyrimidine-2,2',2 '',4,4',4 '',6,6',6 ''-(1H,1'H,1 '' H,3H,3'H,3 '' H,5H,5 '' H)-nonone frameworks in 50-90% yields as a result of the complex electrocatalytic cascade process. Barbiturates, among them condensed barbiturates such as 2'H-5,5':5',5 ''-terpyrimidine-2,2',2 '',4,4',4 '',6,6',6 ''-1H,1'H,1 '' H,3H,3'H,3 '' H,5H,5 '' H)-nonone frameworks are a perspective class of compounds with interesting pharmacological and physiological activity. The application of the effective electrocatalytic cascade method to the formation of medicinally relevant 2'H-5,5':5',5 ''-terpyrimidine-2,2',2 '',4,4',4 '',6,6',6 ''-(1H,1'H,1 '' H,3H,3'H,3 '' H,5H,5 '' H)-notione frameworks is also beneficial from the viewpoint of diversity-oriented large-scale processes and represents novel, facile and environmentally benign synthetic concept for electrocatalytic cascade reaction strategy. (C) 2012 Elsevier B.V. All rights reserved.