The development of novel methodologies to form carbon− sulfur bonds is crucial for the synthesis and derivatization of target molecules in pharmaceutical and material science.1 Important classes of sulfur-containing compounds are biaryl sulfides and their higher oxidized homologues. For that purpose, several methods have been described utilizing transition metal2 or transition-metal-free3 conditions to prepare the biaryl thioether moiety. Most of these approaches predominantly tackle the problem to generate the carbon− sulfur bond (e.g., by nucleophilic aromatic substitution), generating one bond in one step. However, it is desirable to find novel synthetic methods to install additional functionalities concomitant with the formation of the carbon−sulfur bond. Recently, transition-metal catalyzed intramolecular oxycyanation and aminocyanation4 reactions of alkenes and intermolecular cyanothiolation5 of terminal alkynes were reported. After the cleavage of the Het−CN bond, new C−Het and C− CN bonds were formed.