The nonaccessibility of phenyl cations by irradiation of electron-poor aryl chlorides was circumvented by transforming the carbonyl group of aromatic ketones or aldehydes into the corresponding 1,3-dioxolanes and the carboxyl group of benzoate ester into an orthoester functionality. This transformation allowed the heterolytic photoactivation of the Ar-Cl bond in protic media and the generation of phenyl cations. In the presence of π-bond nucleophiles, arylated products were obtained in good to excellent yields.
