Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO2

Nature Communications

Zhen Zhang¹  Li-Li Liao²  Guo-Quan Sun²  Wei Zhang²  Zi-Hao Nie²  Jin-Gui Wu²  Li Li²  Da-Gang Yu³ 

[1] College of Pharmacy and Biological Engineering, Chengdu University, 610041, Chengdu, China;Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 610064, Chengdu, China;Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 610064, Chengdu, China;Beijing National Laboratory for Molecular Sciences, 100190, Beijing, P. R. China;

DOI  :  10.1038/s41467-021-27437-8

来源: Springer

【 摘 要 】

Electrochemical catalytic reductive cross couplings are powerful and sustainable methods to construct C−C bonds by using electron as the clean reductant. However, activated substrates are used in most cases. Herein, we report a general and practical electro-reductive Ni-catalytic system, realizing the electrocatalytic carboxylation of unactivated aryl chlorides and alkyl bromides with CO2. A variety of unactivated aryl bromides, iodides and sulfonates can also undergo such a reaction smoothly. Notably, we also realize the catalytic electrochemical carboxylation of aryl (pseudo)halides with CO2 avoiding the use of sacrificial electrodes. Moreover, this sustainable and economic strategy with electron as the clean reductant features mild conditions, inexpensive catalyst, safe and cheap electrodes, good functional group tolerance and broad substrate scope. Mechanistic investigations indicate that the reaction might proceed via oxidative addition of aryl halides to Ni(0) complex, the reduction of aryl-Ni(II) adduct to the Ni(I) species and following carboxylation with CO2.

【 授权许可】

CC BY