Photochemical Synthesis of Anilines via Ni-Catalyzed Coupling of Aryl Halides with Ammonium Salts
Geyang Song, Ding‐Zhan Nong, Qi Li, Yonggang Yan, Gang Li, Juan Fan, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Abstract
Easy, efficient, and economic synthesis of anilines remains an important challenge in synthetic chemistry. In this study, a Ni(OAc)2-bipyridine complex is shown to readily catalyze the amination of aryl halides with ammonium salts under direct excitation of light, allowing a broad array of aryl chlorides and bromides to be converted into the corresponding primary (hetero)arylamines in the absence of an external photosensitizer. Late-stage modification of drug molecules and 15N-labeling of primary aryl amines are also demonstrated with a number of examples. Photoinduced generation of Ni(I)-bipyridine species is believed to be the key step in the reaction, enabling a Ni(I)/Ni(III) cycle for catalytic turnover.