Forging C−S Bonds Through Decarbonylation: New Perspectives for the Synthesis of Privileged Aryl Sulfides

Aryl thioethers are tremendously important motifs in various facets of chemical science. Traditional technologies for the precise assembly of aryl thioethers rely on transition-metal-catalyzed cross-coupling of aryl halides; however, despite the continuous advances, the scope of these methods remains limited. Recently a series of reports has advanced an alternative manifold in which thio(esters) are subject to transition-metal-catalyzed decarbonylation, which (1) permits to exploit ubiquitous carboxylic acids as highly desirable and orthogonal precursors to aryl halides; (2) overcomes the issues of high concentration of thiolate anion leading to catalyst poisoning; (3) enables for novel disconnections not easily available from aryl halides; and (4) introduces new concepts in catalysis.