Huang Yuan-Qiong, Zhu Li, Mei Tian-Sheng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, Shanghai, China.
Nat Commun. 2025 Apr 30;16(1):4073. doi: 10.1038/s41467-025-59405-x.
Transition metal-catalyzed electrochemical C-H annulation with alkynes has emerged as a promising method for constructing heterocycles via formal cycloadditions. However, catalytic electrochemical C-H annulation with alkenes has been less explored. In this study, we report a cathodic oxygen reduction-enabled rhodium catalyzed (5 + 1) annulation reaction between readily available alkenylphenols and alkenes, yielding valuable 2-substituted 2H-chromenes. Unlike existing methods that involve direct oxidation of catalysts at the anode, our protocol uses a sacrificial anode to protect the substrate from overoxidation, while the cathode reduces oxygen, coupling with the Rh. to regenerate the rhodium catalyst. This efficient, atom-economical heterocyclization reaction demonstrates a broad scope and functional-group tolerance for diverse biologically relevant molecules, with a Faradaic efficiency greater than 100%.
过渡金属催化的电化学炔烃C-H环化反应已成为一种通过形式上的环加成反应构建杂环的有前景的方法。然而，催化电化学烯烃C-H环化反应的研究较少。在本研究中，我们报道了一种由阴极氧还原实现的铑催化的、易于获得的烯基酚与烯烃之间的(5 + 1)环化反应，生成有价值的2-取代2H-色烯。与现有在阳极直接氧化催化剂的方法不同，我们的方案使用牺牲阳极来保护底物不被过度氧化，同时阴极还原氧气，与铑耦合以再生铑催化剂。这种高效、原子经济的杂环化反应对多种具有生物学相关性的分子具有广泛的适用范围和官能团耐受性，法拉第效率大于100%。
Zotero 插件
