TY - JOUR
T1 - Ag(I)-C–H Activation Enables Near-Room Temperature Direct α-Arylation of Benzo[b]thiophenes
AU - Colletto, Chiara
AU - Panigrahi, Adyasha
AU - Fernandez-casado, Jaime
AU - Larrosa, Igor
PY - 2018
Y1 - 2018
N2 - 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.
AB - 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.
U2 - 10.1021/jacs.8b05361
DO - 10.1021/jacs.8b05361
M3 - Article
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -