Pd(II)-catalyzed intermolecular arylation of unactivated C(sp3)-H bonds with aryl bromides enabled by 8-aminoquinoline auxiliary.
Pd(II)-catalyzed intermolecular arylation of unactivated C(sp3)-H bonds with aryl bromides enabled by 8-aminoquinoline auxiliary.
复制标题
DOI：
10.1021/ol500745t
复制
发表时间：
2014-03
期刊：
影响因子：
5.2
通讯作者：
Yu Wei;Huarong Tang;Xuefeng Cong;Bin Rao;Chao Wu;Xiaoming Zeng
中科院分区：
文献类型：
--
作者：
Yu Wei;Huarong Tang;Xuefeng Cong;Bin Rao;Chao Wu;Xiaoming Zeng
描述了在Pd（II）催化的未活化的C（sp（3））-H键的分子间芳基化中使用容易获得的、反应性较低的芳基溴化物作为芳基化试剂的实例。该反应由关键的8-氨基喹啉基导向基团和K2 CO 3碱促进，使得能够在羧酰胺的β-位上区域特异性地安装芳基支架。通过DFT计算的机理研究揭示了C（sp（3））-H活化主导的途径，其特征在于氧化加成作为最高能量过渡态。
An example of using readily available, less reactive aryl bromides as arylating reagents in the Pd(II)-catalyzed intermolecular arylation of unactivated C(sp(3))-H bonds is described. This reaction was promoted by a crucial 8-aminoquinolinyl directing group and a K2CO3 base, enabling regiospecific installation of an aryl scaffold at the β-position of carboxamides. A mechanistic study by DFT calculations reveals a C(sp(3))-H activation-led pathway featuring the oxidative addition as the highest energy transition state.