AbstractHeteroannulation ofN‐Benzyl cyanoacetamide1to a new series of heterocycles has been developed. Thus, reaction of1with different polarized π systems afforded pyrrolo4, pyridone6, pyridine8, and diazapene10derivatives, respectively.N‐Benzyl cyanoacetamide that undergo condensation reaction with salicylaldehyde yielded pyran derivative11. Nitrosation of11furnished condensed pyran13. Compound11reacted with benzaldehyde, carbon disulfide (cyclizing agent), and ammonium thiocyanate to provide pyrane17, thiazine18, and thiourea20derivatives, respectively. Cinnamoyl isothiocyanate was reacted with compound11to produce non‐isolable thiourea derivative21. The newly synthesized compounds have been characterized by infrared (IR), proton nuclear magnetic resonance (1H NMR), and carbon nuclear magnetic resonance (13C NMR) spectral data. The compounds were then evaluated for antibacterial and anticancer activities.