Nickel-Catalyzed 6- <i>endo</i> - <i>trig</i> Reductive Heck Cyclization of Vinyl Fluorides to Access 3-Fluorinated Dihydroquinolinones

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.