Herein, a one-pot protocol to synthesize tetracyclic triazole−piperazine−quinazolinone-fused N-heterocyclic scaffolds is reported. In this strategy, a tandem approach of two highly efficient synthetic reactions, click and cross-dehydrogentive coupling reactions, with high atom economy were employed to obtain the target N-fused scaffolds. Being highly functional group tolerable, this method has broad substrate scope. Interestingly, some of these derivatives showed strong white solid-state fluorescence.

Regioselective synthesis of N‐fused benzimidazo‐indolo‐isoquinoline heterocycles via Pd‐catalyzed domino coupling reaction of 1‐(1‐methyl‐1H‐indol‐2‐yl)‐1H‐benzimidazoles and aryl halides was developed. This one pot methodology proceeded via a five‐member carbopalladacycle intermediate and provided direct and facile route to access structurally complex polyheterocycles in moderate to good yields. These unique hybrid molecules resembled structural similarity with naturally isolated alkaloids. Notably, the present domino process occurred through activation of three C−H bonds and the simultaneous formation of two new C−C bonds in one‐shot. These molecules exhibited strong solid and solution phase fluorescence and their emission spectra in both the medium are reported here.