The chemical evolution of extraterrestrial environments leads to the formation of polycyclic aromatic hydrocarbons (PAHs) via gas phase radical mediated aromatization reactions. We review that these de facto barrierless reactions are capable of forming prebiotic molecules such as nitrogen substituted PAHs (NPAHs), which represent the missing link between nitrogen bearing acyclic molecules and prebiotic nucleobases along with vitamins found in meteorites. Crucial routes leading to the incorporation of nitrogen atoms into the aromatic ring have been exposed. Pyridine can be formed from the reaction of abundant vinyl cyanide and its radical or via cyano radicals reacting with 1,3-butadiene. The NPAHs 1,4-dihydro(iso)quinoline and (iso)quinoline can be synthesized through reaction of pyridyl radicals with 1,3-butadiene or sequentially with two acetylene molecules, respectively. The inclusion of nitrogen into an aromatic system and their growth can fill the mechanistic gaps missing leading from acyclic nitrogen-bearing molecules via pyridine to NPAH-type molecules in the interstellar medium.