Oxygen Vacancy Boosts Nitrogen-Centered Radical Coupling Initiated by Primary Amine Electrooxidation
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2024-11-22 |
| Journal | Journal of the American Chemical Society |
| Authors | Mengwei Han, Yongxiang Luo, Leitao Xu, Wei Chen, Chengmei Li |
| Institutions | National Synchrotron Radiation Research Center, Hunan University |
| Citations | 17 |
Abstract
Section titled âAbstractâSynthesis of nitrogen-centered radicals (NCRs) for radical coupling reactions is a powerful and versatile tool in the arsenal of organic synthetic chemistry. However, there are few reports on the direct synthesis of NCRs based on aqueous electrocatalysis. Herein, we present a new electrochemical primary amine oxidation reaction (ePAOR) system with R<sub>1</sub>R<sub>2</sub>-CH-NH<sub>2</sub> as the substrate for synthesizing NCRs and N-N coupling products. However, ePAOR on the model catalyst (NiO) suffers from low N-N coupling selectivity due to the weak adsorption energy of imine (R<sub>1</sub>R<sub>2</sub>-CâNH) intermediates. Guided by theoretical calculations, the oxygen vacancy gives NiO a strong adsorption capacity of R<sub>1</sub>R<sub>2</sub>-CâNH so that it boosts nitrogen-centered radical coupling initiated by the ePAOR on oxygen vacancy-rich NiO (V<sub>O</sub>-NiO), and the effective utilization rate of NCRs was increased from 36 to 75%. This approach is compatible with a wide range of primary amines and can be applied to N-N cross-coupling systems as well.