Zhang Xuemeng, Zhang Yiteng, Li Mengfan, Yan Qibo, Lu Weifeng, Zhu Jun-Jie, Cheng Xu, Min Qianhao
State Key Laboratory of Analytical Chemistry for Life Science, Chemistry and Biomedicine Innovation Center, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, PR China.
Shenzhen Research Institute of Nanjing University, Shenzhen, PR China.
Nat Commun. 2025 Aug 12;16(1):7452. doi: 10.1038/s41467-025-62677-y.
Rapid reaction screening and in-depth mechanistic exploration of electroorganic synthesis remain challenging due to low throughput of experimentation and high complexity of electrode and homogenous processes. Here, we report a decoupled electrochemical flow microreactor hyphenated mass spectrometry (namely DEC-FMR-MS) platform for high-throughput reaction screening and intermediate tracking of electrosynthesis. This platform combines in-capillary electrochemical transformation with operando MS interrogation, enabling rapid reactivity survey of a series of electrosynthetic reactions on nanomole scale. Moreover, the spatial decoupling design allows segmented dissection of short-lived intermediates involved pathways in interfacial electrochemical and homogenous chemical events, which are initially interwoven in reaction networks. The utility of this platform is highlighted by 1) discovery and verification of quasi-electrocatalytic pathways in electrooxidative C-H/N-H cross-coupling, 2) kinetic measurements of TEMPOH-mediated dehydrogenation of N-heterocycles, and 3) mapping the landscape of intermediates (alkene radical cation and nitrene) in electrochemical aziridination.
由于实验通量低以及电极和均相过程的高度复杂性，电有机合成的快速反应筛选和深入机理探索仍然具有挑战性。在此，我们报道了一种用于电合成高通量反应筛选和中间体追踪的解耦电化学流动微反应器联用质谱（即DEC-FMR-MS）平台。该平台将毛细管内电化学转化与原位质谱检测相结合，能够在纳摩尔规模上对一系列电合成反应进行快速反应性研究。此外，空间解耦设计允许对界面电化学和均相化学事件中涉及的短寿命中间体的反应途径进行分段剖析，这些反应途径最初在反应网络中相互交织。该平台的实用性体现在以下几个方面：1）在电氧化C-H/N-H交叉偶联中发现并验证准电催化途径；2）对TEMPOH介导的N-杂环脱氢进行动力学测量；3）绘制电化学氮杂环丙烷化反应中中间体（烯烃自由基阳离子和氮烯）的图谱。
