Catalytic Oxidative C–H Annulation of Arylthiol Derivatives with 1,3-Diynes toward 3,3′-Bibenzothiophenes

Disclosed herein is a catalytic oxidative C–H annulation of thiophenol derivatives with 1,3-diynes, which provides an efficient synthetic approach to both symmetrical and nonsymmetrical 3,3′-bibenzothiophenes. This protocol exhibits a broad substrate scope, excellent functional group tolerance, high regioselectivity, and catalyst-enabled switchable mono/diannulation selectivity. Moreover, three novel helical-type bithiophene heptagonal imides, which are potentially applicable in optoelectronic materials, are constructed based on this reaction.