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

Beibei Zhang; Xuemin Li; Xiaoxian Li; Zhenyang Yu; Bingyue Zhao; Xiaofan Wang; Yunfei Du; Kang Zhao

doi:10.1021/acs.joc.1c02404

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

J Org Chem. 2021 Dec 3;86(23):17274-17281. doi: 10.1021/acs.joc.1c02404. Epub 2021 Nov 22.

Authors

Beibei Zhang¹, Xuemin Li¹, Xiaoxian Li¹, Zhenyang Yu¹, Bingyue Zhao¹, Xiaofan Wang¹, Yunfei Du¹, Kang Zhao²

Affiliations

¹ Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China.
² State Key Laboratory of Microbial Technology, Institute of Microbial Technology, Shandong University, Qingdao 266237, China.

PMID: 34806887
DOI: 10.1021/acs.joc.1c02404

Abstract

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.