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

作者：Ichitsuka Tomohiro; Takanohashi Tsuyoshi; Fujita Takeshi; Ichikawa Junji^*

来源：Journal of Fluorine Chemistry, 2015, 170: 29-37.

DOI：10.1016/j.jfluchem.2014.12.003

• Difluoroalkene
• Organozinc
• Cross-coupling reaction
• Palladium
• Copper
• Catalyst

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.

• 出版日期2015-2