Dearomatization/Spiroannulation of Halophenols Enables the Forging of Contiguous Quaternary Carbon Cyclohexadienones.

A dearomatization/spiroannulation process has been successfully achieved between simple halophenols and α,β-unsaturated olefins under mild reaction conditions. This transformation addresses the chemoselectivity issue in the dearomatizative transformation of phenol scaffolds (6π-electron) caused by the SE Ar process, enabling the construction of versatile cyclohexadienone frameworks containing contiguous quaternary all-carbon centers in high yields. Further studies have provided valuable insights into the process, revealing that debromination/spiroannulation occurs through the S RN 1 pathway.