TiCl4 and Grignard reagent-promoted ring-opening reactions of various epoxides: synthesis of γ-hydroxy-α,α-difluoromethylenephosphonates

A straightforward methodology for the synthesis of diethyl γ-hydroxy-α,α-difluoromethylenephosphonates is reported. In the presence of titanium tetrachloride, epoxide ring-opening reactions occurred upon treatment with lithium diethyl difluoromethylenephosphonate. When diethyl 3,4-epoxy-1,1-difluorobutylphosphonate was reacted with TiCl4 and Grignard reagents, the corresponding halohydrins were obtained in very good yields.