AbstractThe selective conversion of 1,2‐bis(1′‐acetoxy‐2′‐ propynyl)benzene derivatives to the corresponding 1,2‐diallenylbenzenes with the aid of a palladium(O)–samarium(II) reduction system leads to a new route to fairly reactive o‐naphthoquinodimethane derivatives under mild conditions. The reactions of these naphthoquinodimethanes were found to follow different paths depending on the nature of the substituents on the terminal acetylenic carbon atoms. They undergo intermolecular Diels–Alder reactions with various dienophiles, intramolecular [2+2] cycloadditions, or intramolecular [1,5]‐sigmatropic hydrogen shifts.