Abstract: | A highly chemoselective method for the synthesis of heterocyclic [3.3.3]propellane derivatives was developed via sequential three‐component reactions of acenaphthenequinone, malononitrile/cyanoacetate and a variety of 1,3‐dicarbonyl compounds under mild conditions in ethanol. A plausible mechanism for this type of reaction was proposed. The value of this method was highlighted by its high selectivity, simple procedures, and good yields. |