10.1021/acs.joc.6b01933.s002
Naveen
Naveen
Vadla Rajkumar
Vadla
Rajkumar
Srinivasarao Arulananda Babu
Srinivasarao Arulananda
Babu
Bojan Gopalakrishnan
Bojan
Gopalakrishnan
Pd(II)-Catalyzed Bidentate
Directing Group-Aided Chemoselective
Acetoxylation of Remote ε‑C(sp<sup>2</sup>)–H
Bonds in Heteroaryl–Aryl-Based Biaryl Systems
American Chemical Society
2016
biaryl substrate 2
C -3 arylated furfurylamines
activation
BDG-aided chemoselective acetoxylation
carboxamide systems
bond
Pd
bidentate
thiophen -2-ylmethanamines
chemoselective acetoxylation
functionalization
ε-
2016-11-18 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Pd_II_-Catalyzed_Bidentate_Directing_Group-Aided_Chemoselective_Acetoxylation_of_Remote_C_sp_sup_2_sup_H_Bonds_in_Heteroaryl_Aryl-Based_Biaryl_Systems/4290944
In
this Article, we report our successful attempt on the Pd(II)-catalyzed,
bidentate directing group-aided, chemoselective acetoxylation/substitution
of remote ε-C(sp<sup>2</sup>)–H bonds using heteroaryl–aryl-based
biaryl systems. While the bidentate directing group (BDG)-aided, C–H
activation, and functionalization/acetoxylation of the β-, γ-,
and δ-C–H bonds of the appropriate carboxamide systems
were well documented, there exist only rare reports dealing with the
C–H activation and functionalization of remote ε-C–H
bonds of appropriate substrates. Especially, the BDG-aided chemoselective
acetoxylation of the remote ε-C(sp<sup>2</sup>)–H bond
over cyclization has not been explored well. Accordingly, in this
work, the treatment of various picolinamides/oxalylamides/pyrazine-2-carboxamides <b>4</b>/<b>7</b>/<b>9</b>/<b>11</b>, which were
derived from the corresponding C-3 arylated furfurylamines or thiophen-2-ylmethanamines
with PhI(OAc)<sub>2</sub> in the presence of the Pd(OAc)<sub>2</sub> catalyst, successfully afforded the corresponding ε-C–H
acetoxylated products. The chemoselective acetoxylation of the ε-C–H
bond was possible and facilitated by the biaryl substrate <b>4</b>/<b>7</b>/<b>9</b>/<b>11</b> and not by the biaryl
substrate <b>2a</b>.