Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

Described herein is a decarbonylative tandem C–H bis-arylsulfenylation of indole at the C2 and C4 C–H bonds through the use of pentamethylcyclopentadienyl iridium dichloride dimer ([Cp*IrCl 2 ] 2 ) catalyst and disulfides. A new sacrificial electron-rich adamantoyl-directing group facilitates indole C–H bis-functionalization with a traceless in situ removal. Various differently substituted disulfides can be easily accommodated in this reaction by a coordination to Ir(III) through the formation of six- and five-membered iridacycles at the C2 and C4 positions, respectively. Mechanistic studies show that a C–H activation-induced C–C activation is involved in the catalytic cycle.