Lin Qifeng, Duan Yingdong, Li Yao, Jian Ruijun, Yang Kai, Jia Zongbin, Xia Yu, Zhang Long, Luo Sanzhong
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, China.
MOE Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department of Chemistry, Tsinghua University, Beijing, China.
Nat Commun. 2024 Aug 12;15(1):6900. doi: 10.1038/s41467-024-50945-2.
Electrochemical reactions via carbocation intermediates remain fundamental transformations that build up molecular functionality and complexity in a sustainable manner. Enantioselective control of such processes is a great challenge in a highly ionic electrolyte solution. Here, we report an anodic generation of chiral α-imino carbocation intermediates by enamine catalysis. The chiral carbocation intermediates can be intercepted by a variety of nucleophiles such as alcohols, water and thiols with high stereoselectivity. The key S1 step proceeds via a tertiary amine-mediated proton shuttle that facilitates facial selection in reacting with carbocation.
通过碳正离子中间体进行的电化学反应仍然是可持续构建分子功能和复杂性的基本转化过程。在高离子电解质溶液中，对这类过程进行对映选择性控制是一项巨大挑战。在此，我们报道了通过烯胺催化阳极生成手性α-亚氨基碳正离子中间体。手性碳正离子中间体能够被多种亲核试剂如醇、水和硫醇以高立体选择性截获。关键的S1步骤通过叔胺介导的质子穿梭进行，这有利于在与碳正离子反应时进行面选择性。
