Privileged scaffolds play a vital role in both rational drug design and materials science, with nitrogen-containing heterocycles representing a premier class of functional molecules. In this context, our group has demonstrated a modular approach for the synthesis of diverse N-heterocyclic small molecules starting from readily accessible imino ketones. Utilizing an earth-abundant calcium catalyst and common chemical feedstocks, this strategy employs a cascade Friedel-Crafts arylation followed by (3+2) or (4+2) cyclizations to deliver fully substituted pyrroles, indoles, and pyrroloquinolines. Furthermore, this synthetic platform is extended to demonstrate a unique 1,2-mutual group transfer reaction and C–H functionalizations utilizing DACs, highlighting its broad synthetic utility.