Direct Bis-Alkyl Thiolation for Indoles with Sulfinothioates under Pummerer-Type Conditions.

A base-free bis-alkyl thiolation reaction of indoles with sulfinothioates under Pummerer-type conditions is described. Sulfinothioates, activated with 2,2,2-trifluoroacetic anhydride, are demonstrated to be an efficient thiolation reagent for wide applications. This approach enabled double C-H thiolation at the C2 and C3 of the indole in one pot. The mechanism studies suggested the thiolation was realized through the sulfoxonium salt rather than sulfenyl carboxylate.