Base-Free Hiyama Coupling Reaction via a Group 10 Metal Fluoride Intermediate Generated by C–F Bond Activation

A Pd(0)-catalyzed Hiyama coupling reaction of tetrafluoroethylene (TFE) proceeded without the use of a base to give α,β,β-trifluorostyrene derivatives. A Ni(0)-catalyzed Hiyama coupling reaction of perfluoroarenes also occurred without a base. The key intermediate in these reactions would be a transition-metal fluoride complex that is generated in situ by the oxidative addition of a C–F bond.