Application of Fundamental Organometallic Chemistry to the Development of a Gold‐Catalyzed Synthesis of Sulfinate Derivatives

The development of a gold(I)‐catalyzed sulfination of aryl boronic acids is described. This transformation proceeds through an unprecedented mechanism which exploits the reactivity of gold(I)–heteroatom bonds to form sulfinate anions. Further in situ elaboration of the sulfinate intermediates leads to the corresponding sulfones and sulfonamides, two pharmacophores routinely encountered in drug discovery.