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

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 unpreceden...

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Veröffentlicht in:Journal of the American Chemical Society 2018-08, Vol.140 (30), p.9638-9643
Hauptverfasser: Colletto, Chiara, Panigrahi, Adyasha, Fernández-Casado, Jaime, Larrosa, Igor
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container_issue 30
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container_title Journal of the American Chemical Society
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creator Colletto, Chiara
Panigrahi, Adyasha
Fernández-Casado, Jaime
Larrosa, Igor
description 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.
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title Ag(I)–C–H Activation Enables Near-Room-Temperature Direct α‑Arylation of Benzo[b]thiophenes
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