Activation of organosilicon compounds with fluoride ion produces a transient pentacoordinate silicate, which is capable of transmetalation with a catalytic organopalladium complex and achieves cross-coupling reaction. Mono-, di- or trifluorosilanes can deliver alkenyl, aryl, or alkyl group, respectively. The reaction, characterized by high chemo- and stereoselectivity, was successfully applied to synthesis of HMG-CoA reductase inhibitor NK-104 and functionalized biaryls for liquid crystals. The stereochemical aspects are discussed.