Ag(I)–C–H Activation Enables Near-Room-Temperature Direct α‑Arylation of Benzo[b]thiophenes

The first example of near-room-temperature α-arylation of benzo­[b]­thiophenes is reported. The discovery rests on the observation of a switch in α-/β-regioselectivity at different loadings of Pd2(dba)3·CHCl3 in the coupling between benzo­[b]­thiophene and 4-iodotoluene. We show that this unprecedented regioselectivity switch is driven by a Ag­(I)-mediated C–H activation at the α-C–H position, which becomes the dominant mode of reactivity at low concentrations of Pd. Competition experiments, kinetic studies, KIE, and D/H scrambling experiments have been carried out supporting this mechanism.