An Interrupted Pummerer Reaction Mediated by a Hypervalent Iodine(III) Reagent: In Situ Formation of RSCl and Its Application for the Synthesis of 3-Sulfenylated Indoles

An interrupted Pummerer reaction of PhICl2 and sulfoxides was found to in situ generate reactive organosulfenyl chloride, which enabled the intramolecular electrophilic cyclization of 2-alkynylanilines, generating 3-sulfenylated indole with a good to excellent yield under metal-free conditions. One striking feature of the approach is that sulfoxide regeneration can be realized via the oxidation of the formed sulfides by the generated hypervalent iodine species.