Heteroannulation of N-Benzyl cyanoacetamide 1 to a new series of heterocycles has been developed. Thus, reaction of 1 with different polarized π systems afforded pyrrolo 4, pyridine 6, pyridine 8, and diazapene 10 derivatives, respectively. N-Benzyl cyanoacetamide that undergo condensation reaction with salicylaldehyde yielded pyran derivative 11. Nitrosation of 11 furnished condensed pyran 13. Compound 11 reacted with benzaldehyde, carbon disulfide (cyclizing agent), and ammonium thiocyanate to provide pyrane 17, thiazine 18, and thiourea 20 derivatives, respectively. Cinnamoyl isothiocyanate was reacted with compound 11 to produce nonisolable thiourea derivative 21. 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.