Iodine(III) Enabled Dehydrogenative Aryl C-S Coupling by insitu Generated Sulfenium Ion

Due to the normal polarity preferences, arenes form stable complexes with thiols through S-H 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 insitu 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.