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

Abstract

Abstract Due to the normal polarity preferences, arenes form stable complexes with thiols through S−H⋅⋅⋅π interaction and direct dehydrogenative aryl C−S coupling is usually restricted. We report here an umpolung based one pot and direct C−S 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 C−S 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. magnified image