[structure: see text] An unexpected discovery of a novel cyclocondensation reaction of 1,8-diazabicyclo[5.4.0]undec-8-ene (DBU) with activated 1,2-dichloro compounds is described. The 2-aminopyrrole skeleton is generated through the concomitant formation of new nitrogen-carbon and carbon-carbon bonds. A new pentacyclic derivative formed upon the reaction of 2,3-dichloroquinoxaline with DBU exhibits strong fluorescence both in solutions (Phi in hexane = 0.4) and in the solid state.