Cu(ii)-catalyzed sulfide construction: both aryl groups utilization of intermolecular and intramolecular diaryliodonium saltElectronic supplementary information (ESI) available. CCDC 1428271. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6cc09201b

A sulfur-iodine exchange protocol of diaryliodonium salts with inorganic sulfur salt was developed. Both aryl groups in the diaryliodonium salt were fully exerted in this transformation. Five- to eight-membered sulfur-containing heterocycles were achieved. Note that [1]benzothieno-[3,2- b ][1]benzothiophene (BTBT) (an organic field-effect transistor (OFET) material) and Zaltoprofen were efficiently established through this method. A sulfur-iodine exchange strategy was developed that utilized both aryl groups of diaryliodonium salt employed in intermolecular and intramolecular reactions.