Synthesis of complex, multiring, spirocyclic, 1,3-dicarbonyl fused, and highly functionalized 5-phenyl-1-azabicyclo[3.1.0]hexanes (ABCH) has been achieved by an intermolecular reaction of 2-(2′-ketoalkyl)-1,3-indandiones or α,γ-diketo esters with (1-azidovinyl)benzenes under transition metal-free conditions. The reaction proceeds in a highly diastereoselective manner with a wide range of functional groups and provides moderate to good yields. Additionally, we have studied the preliminary biological activities of a few synthetic compounds against HeLa and triple-negative breast cancer (TNBC) cell lines.