Cobalt‐Catalyzed Intramolecular Markovnikov Hydrocarbonylation of Unactivated Alkenes via Hydrogen Atom Transfer

作者：Donghao Jiang, Xinzhu Li, Mengdie Xiao, Li‐Jie Cheng · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202412828 · 被引用次数：21 · 研究领域：Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis、Asymmetric Synthesis and Catalysis

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.