A variety of dearomatized compounds have been prepared in moderate to excellent yields from planar scaffolds using trichloroisocyanuric acid (TCCA) as an atom-economical chlorinating agent. The method tolerates a broad range of functionalities and can take place in several green and/or sustainable solvents. Twenty-one examples of 1,1-dichlorinated products of dearomatized 2-naphthols and analogous heteroarenes (quinolinols, isoquinolinols, and quinazolinol) are reported along with five examples of monochlorinated dearomatized products. The utility of the 1,1-dichloronaphthalenone product as a reactive intermediate species is demonstrated in a two-step, one-pot reaction carried out in a green solvent. In a mechanistic investigation, the coordination of the chlorinating agent to the hydroxy substituent of the planar scaffold prior to chlorine transfer is implicated.
