Cai Yue-Ming, Liu Xiao-Ting, Xu Lin-Lin, Shang Ming
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, P. R. China.
Angew Chem Int Ed Engl. 2024 Mar 18;63(12):e202315222. doi: 10.1002/anie.202315222. Epub 2024 Feb 19.
A new electrochemical transformation is presented that enables chemists to couple simple alkyl carboxylic acid derivatives with an electrophilic amine reagent to construct C(sp )-N bond. The success of this reaction hinges on the merging of cooperative electrochemical reduction with nickel catalysis. The chemistry exhibits a high degree of practicality, showcasing its wide applicability with 1°, 2°, 3° carboxylic acids and remarkable compatibility with diverse functional groups, even in the realm of late-stage functionalization. Furthermore, extensive mechanistic studies have unveiled the engagement of alkyl radicals and iminyl radicals; and elucidated the multifaceted roles played by Pr O, Ni catalyst, and electricity.
本文介绍了一种新的电化学转化方法，该方法使化学家能够将简单的烷基羧酸衍生物与亲电胺试剂偶联，以构建C(sp³)-N键。该反应的成功取决于协同电化学还原与镍催化的结合。这种化学方法具有高度的实用性，对伯、仲、叔羧酸都有广泛的适用性，并且与各种官能团具有显著的兼容性，甚至在后期官能团化领域也是如此。此外，广泛的机理研究揭示了烷基自由基和亚胺基自由基的参与；并阐明了PrOⁱ、镍催化剂和电所起的多方面作用。
