Solvent-free base-controlled addition reaction of H -phosphonates and H -phosphine oxides to α-CF 3 styrenes: facile synthesis of β-CF 3 -substituted phosphonates and phosphine oxides.

A practical and efficient solvent-free synthesis of β-trifluoromethyl-substituted phosphonates and phosphine oxides via hydrophosphonylation and hydrophosphinylation of α-(trifluoromethyl)styrenes with H -phosphonates and H -phosphine oxides, respectively, was developed. The reaction proceeded smoothly within 2 h at room temperature without the cleavage of the rather fragile C-F bond in α-(trifluoromethyl)styrenes and afforded a wide variety of structurally diverse and valuable β-trifluoromethyl-containing phosphonates and phosphine oxides in moderate to good yields. This protocol features mild conditions, wide substrate scope, simple manipulation, and excellent functional group compatibility.