Nickel-Catalyzed 6-endo-trig Reductive Heck Cyclization of Vinyl Fluorides to Access 3-Fluorinated Dihydroquinolinones.

作者：Juanjuan Zhang, Tangji Chen, Yingyu Yang, Yunfeng Chen, Wanyu Huang, Wei-Guang Yang, Weigao Hu, Wangqing Kong, Jia Zheng · 发表于：Organic Letters · 年份：2026 · DOI：10.1021/acs.orglett.6c02087 · 研究领域：Medicine

Intramolecular carbometalation-based difunctionalizations of alkenes have been well-developed. In most of the processes, the 5-exo-trig cyclization is highly favored over the 6-endo-trig carbometalation. Furthermore, fluorinated alkenes are still unexplored in these reactions due to the β-F elimination of the alkyl metal species. Herein, we report a dual ligand catalytic system for the 6-endo-trig reductive Heck reaction, which might undergo nickel-based dyotropic rearrangement. This methodology allowed rapid synthesis of 3-F-dihydroquinolinones, showing good tolerance of functionality and compatibility of various bioactive skeletons. This reaction expands the α substituents of alkenes from alkyl/aryl groups to challenging fluoride, which also opens up a new possibility for the intramolecular difunctionalizations of vinyl fluoride.