Iodine(III) Enabled Dehydrogenative Aryl C−S Coupling by in situ Generated Sulfenium Ion

Abstract

Due to the normal polarity preferences, arenes form stable complexes with thiols through SÀH···p interaction and direct dehydrogenative aryl CÀS coupling is usually restricted. We report here an umpolung based one pot and direct CÀS coupling approach under metal free and mild condition. Electrophile sulfenium ions were generated in situ from thiols using iodine(III) reagent PhI(OAc) 2 (PIDA) and subsequently used for aromatic electrophilic substitution (EArS) to synthesize diaryl sulfides. Also by using of appropriate amount of PIDA, cascaded synthesis of CÀS and S=O bonds led to aryl sulfinyl arenes in one pot. Covalent self-sorting or competitive experiments further confirmed the involvement of sulfenium ion in the EArS.

An Efficient, Sustainable Rhodium‐Catalyzed and Ionic Liquid‐Mediated C−H Thiolation and Selenation of Acetanilide with Diaryl Disulfides and Diaryl Diselenides

“…There was no doubt that the utilization of large amounts of oxidants involving metal salts (Ag I or Cu II ) for this C−H functionalization were detrimental to the environment. In 2018, the Mal group reported a metal‐free dehydrogenative C−S bond formation between arenes and thiols through iodine(III) reagent PIDA [16] . However, several drawbacks still existed owing to the thiols as the reactant possessed bad odor and serious environmental pollution.…”

Iodine-based reagents in photoredox-organocatalysis

“…77 Selective synthesis of sulfoxide molecules is well known in organic chemistry. 78 In 2018, Cai and coworkers developed a method via 1,2-aryl group migration reaction for the synthesis of highly substituted α-aryl-γmethylsulfinyl ketones (Figure 13). 79 In this work they have used the synergic effect of organo-photocatalyst with hypervalent iodine reagent to activate C(sp 3 )-H bond of dimethylsulfoxide (DMSO) under visible light irradiation.…”

Recent Advances in the Synthesis of Sulfides, Sulfoxides and Sulfones via C-S Bond Construction from Non-Halide Substrates

“…In 2018, the Mal group developed a C-S coupling reaction of aryl thiols and benzenes bearing multiple methyl and/or methoxyl groups in the presence of PhI(OAc) 2 in HFIP (Scheme 29) [49]. It is interesting that the product was controlled by the amount of PhI(OAc) 2 .…”