Photoelectrochemical Ni-catalyzed cross-coupling of aryl bromides with amine at ultra-low potential

• Published in: Nature communications Vol. 15; no. 1; pp. 6907 - 8
• Main Authors: Wang, Jinghao, Li, Siyang, Yang, Caoyu, Gao, Huiwen, Zuo, Lulu, Guo, Zhiyu, Yang, Pengqi, Jiang, Yuheng, Li, Jian, Wu, Li-Zhu, Tang, Zhiyong
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 12-08-2024; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 140/58; 147/135; 147/143; 639/638/403/933; 639/638/439/890; 639/638/77/890; Amines; Aniline; Aromatic compounds; Bromides; Catalysis; Catalysts; Chemical synthesis; Clean energy; Cross coupling; Electrochemistry; Energy consumption; Functional groups; Halides; Humanities and Social Sciences; multidisciplinary; Natural products; Oxidation; Photoanodes; Science; Science (multidisciplinary); Silver nitrate; Substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-51333-6

Photoelectrochemical (PEC) cell is an ideal platform for organic transformation because of its green benefits and minimal energy consumption. As an emerging methodology, the reaction types of photoelectrocatalytic organic synthesis (PECOS) are limited to simple oxidation and C–H activation at current stage. Metal catalysis for the construction of C(sp
2
)–N bonds has not been touched yet in PECOS. We introduce here a PEC method that successfully engages Ni catalysis for the mild production of aniline derivatives. Experimental and computational investigations elucidate that the addition of photoanode-generated amine radical to Ni catalyst avoids the sluggish nucleophilic attack, enabling the reaction to proceed at an ultra-low potential (–0.4 V vs. Ag/AgNO
3
) and preventing the overoxidation of products in conventional electrochemical synthesis. This synergistic catalysis strategy exhibits good functional group tolerance and wide substrate scope on both aryl halides and amines, by which some important natural products and pharmaceutical chemicals have been successfully modified.
The reaction types of photoelectrocatalytic organic synthesis (PECOS) are limited to simple oxidation and C–H activation at current stage while metal catalysis for the construction of C(sp2)–N bonds remains unexplored. Here, the authors introduce a PEC method that successfully engages Ni catalysis for the mild production of aniline derivatives.