Xue Wenxuan, Zhu Zhiwei, Chen Sanxia, You Bo, Tang Conghui
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074, China.
State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing 100191, China.
J Am Chem Soc. 2023 Feb 8. doi: 10.1021/jacs.2c12344.
Alkene functionalization with a single-atom catalyst (SAC) which merges homogeneous and heterogeneous catalysis is a fascinating route to obtain high-value-added molecules. However, C-N bond formation of alkene with SAC is still unexplored. Herein, a bimetal-organic framework-derived Co-N/C catalyst with an atomically dispersed cobalt center is reported to show good activity of chemoselective aziridination/oxyamination reactions from alkene and hydroxylamine, and late-stage functionalization of complex alkenes and diversified synthetic transformations of the aziridine product further expand the utility of this method. Moreover, this system proceeds without external oxidants and exhibits mild, atom-economic, and recyclable characters. Detailed spectroscopic characterizations and mechanistic studies revealed the structure of the catalytic center and possible intermediates involved in the mechanism cycle.
利用融合均相和多相催化的单原子催化剂(SAC)对烯烃进行官能团化是获得高附加值分子的一条引人入胜的途径。然而,烯烃与SAC的C-N键形成仍未被探索。在此,报道了一种具有原子分散钴中心的双金属有机框架衍生的Co-N/C催化剂,该催化剂在烯烃和羟胺的化学选择性氮杂环丙烷化/氧胺化反应中表现出良好的活性,复杂烯烃的后期官能团化以及氮杂环丙烷产物的多样化合成转化进一步拓展了该方法的实用性。此外,该体系无需外部氧化剂即可进行反应,具有温和、原子经济和可循环利用的特点。详细的光谱表征和机理研究揭示了催化中心的结构以及机理循环中可能涉及的中间体。