Scheme 4.

Scope III and IV: Construction of polyfluorinated biaryls having a styrene unit (top) and further diversification of coupling products by a Heck reaction (bottom). Regioisomeric ratios (para : ortho : meta) were determined by quantitative ¹⁹F NMR analysis with hexafluorobenzene as an internal standard. Yields are isolated yields of para regioisomers after purification. Reaction conditions for the Heck reaction: iodobenzene (6 a, 1.5 equiv, for 3 ck) or methyl 4‐iodobenzoate (6 b, 1.5 equiv, for 3 dk), Pd(OAc)₂ (2.0 mol%), Et₃N (5.0 equiv), DMF, 100 °C, 20 h.