A general and efficient Cp*CoIII-catalyzed C2-thiolation and C2,C3-dithiolation of indole derivatives has been achieved employing N-(aryl/alkylthio)succinimide as a thiolating reagent. This external oxidant-free method utilizes only catalytic amounts of additive and tolerates various functional groups to afford various thiolated products in good yields. Control experiments revealed the importance of the Cp*CoIII-catalyst for both C2- and C3-thiolation.
