Jiang Donghao, Li Xinzhu, Xiao Mengdie, Cheng Li-Jie
State Key Laboratory of Chemo/Biosensing and Chemometrics College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China.
Angew Chem Int Ed Engl. 2024 Nov 11;63(46):e202412828. doi: 10.1002/anie.202412828. Epub 2024 Sep 23.
A cobalt-catalyzed intramolecular Markovnikov hydroalkoxycarbonylation and hydroaminocarbonylation of unactivated alkenes has been developed, enabling highly chemo- and regioselective synthesis of α-alkylated γ-lactones and α-alkylated γ-lactams in good yields. The mild reaction conditions allow use of mono-, di- and trisubstituted alkenes bearing a variety of functional groups. Preliminary mechanistic studies suggest the reaction proceeds through a CO-mediated hydrogen atom transfer (HAT) and radical-polar crossover (RPC) process, in which a cationic acylcobalt(IV) complex is proposed as the key intermediate.
已开发出一种钴催化的未活化烯烃分子内马氏氢烷氧基羰基化和氢胺羰基化反应，能够以良好的产率高效地化学选择性和区域选择性合成α-烷基化γ-内酯和α-烷基化γ-内酰胺。温和的反应条件允许使用带有各种官能团的单取代、二取代和三取代烯烃。初步机理研究表明，该反应通过CO介导的氢原子转移（HAT）和自由基-极性交叉（RPC）过程进行，其中阳离子酰基钴（IV）配合物被认为是关键中间体。
