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>.