Gold-Catalyzed Intermolecular Alkyne Oxyarylation for C3 Functionalization of Benzothiophenes

C3-selective C-C bond formation on benzothiophenes is challenging, and few direct functionalization methods are available. A gold-catalyzed reaction of alkynes with benzothiophene S -oxides provides regioselective entry into C3-alkylated benzothiophenes with the C7-alkylated isomer as the minor product. This oxyarylation reaction works with alkyl and aryl alkynes and substituted and unsubstituted benzothiophenes. Mechanistic studies identify that sulfoxide inhibits the catalyst [DTBPAu(PhCN)]SbF 6 , which also degrades and forms the unreactive complex [(DTBP) 2 Au]SbF 6 .