A versatile difluorovinylation method: Cross-coupling reactions of the 2,2-difluorovinylzinc–TMEDA complex with alkenyl, alkynyl, allyl, and benzyl halides

•A series of 2,2-difluorovinyl compounds were synthesized via the cross-coupling of a 2,2-difluorovinylzinc–TMEDA complex.•This protocol started from an industrial material, 1,1-difluoroethylene.•The 2,2-difluorovinylzinc–TMEDA complex is thermally stable and storable.

A thermally stable 2,2-difluorovinylzinc–TMEDA complex was prepared via a deprotonation–transmetallation sequence starting from commercially available 1,1-difluoroethylene. The complex thus formed was successfully applied to transition metal-catalyzed cross-coupling reactions with a wide range of organic halides, which led to the syntheses of 2,2-difluorovinyl compounds. On treatment with the difluorovinylzinc–TMEDA complex in the presence of an appropriate palladium or copper catalyst, alkenyl, alkynyl, allyl, and benzyl halides effectively underwent difluorovinylation to afford 1,1-difluoro-1,3-dienes, 1,1-difluoro-1,3-enynes, 1,1-difluoro-1,4-dienes, and (3,3-difluoroallyl)arenes, respectively.

Graphical abstractA series of 2,2-difluorovinyl compounds were synthesized via the Pd- and Cu-catalyzed cross-coupling of a 2,2-difluorovinylzinc–TMEDA complex. The 2,2-difluorovinylzinc–TMEDA complex, prepared from 1,1-difluoroethylene, an industrial material, is thermally stable and storable.Figure optionsDownload full-size imageDownload as PowerPoint slide