Thioether-Directed Peri-Selective C-H Arylation under Rhodium Catalysis: Synthesis of Arene-Fused Thioxanthenes.

A rhodium-catalyzed direct C-H arylation of naphthalene and anthracene was developed with the assistance of a thioether directing group. The reaction proceeded with exclusive peri-selectivity, and the series of coupling products were readily transformed into the corresponding sulfur-containing polyaromatics. Charge-transport properties of the provided dithiapyrenes were evaluated by computational studies.