Three‐component reaction between ninhydrin–phenol adducts, dialkyl acetylenedicarboxylates, and triphenylphosphine was investigated. Utilizing this protocol, dialkyl 10‐oxo‐10H‐4b,9b‐(epoxyethanooxy)indeno[1,2‐b]benzofuran‐12,13‐dicarboxylates as functionalized heterocyclic [4,3,3] propellanes was synthesized in 6‐endo‐trig cyclization mode. 8‐hydroxyquinoline showed serendipitous reactivity and produced para substituted adduct in the reaction with ninhydrin in acetic acid media and hence produced dialkyl 8a‐(4‐(alkoxycarbonyl)‐2‐oxo‐2H‐pyrano[3,2‐h]quinolin‐6‐yl)‐8‐oxo‐8,8a‐dihydro‐2H‐indeno[2,1‐b]furan‐2,3‐dicarboxylate in the reaction with dialkyl acetylenedicarboxylates and PPh3.