Di-tert-butyl Peroxide Promoted Direct CH Arylation of Unactivated Arenes with Aryl Halides

Di‐tert‐butyl peroxide can smoothly promote the coupling of aryl halides with benzene derivatives without the aid of transition‐metal catalysts through a chain homolytic aromatic substitution mechanism in the presence of potassium tert‐butoxide. Radical reasoning: Di‐tert‐butyl peroxide and potassium tert‐butoxide smoothly direct the CH arylation of unactivated benzene derivatives with aryl halides without the aid of a transition metal. Reactions occur through a base‐promoted homolytic aromatic substitution process and involve aryl radicals and aryl radical anions as intermediates. The process to synthesize biaryl compounds is high yielding and practical.