This Perspective provides an overview of transition metal-catalyzed cross coupling reactions of polyfluoroarenes. When appropriate, stoichiometric C-F activation and subsequent reaction are briefly covered.

A readily accessible, user-friendly Pt(II) complex (Cl2Pt(SMe2)2, 2) shows good reactivity for selective, catalytic methylation of polyfluoroarylimines.

A Ni-catalyzed, chemoselective cross-coupling reaction of polyfluoroarenes under mild reaction conditions is reported. A variety of fluorine-containing biaryls are synthesized in good-to-excellent yields. A wide range of substitution patterns and functional groups are tolerated.

We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks.

We recently reported methods for the catalytic methylation and methoxylation of polyfluoroaryl imines utilizing [Pt 2 Me 4 (SMe 2 ) 2 ] as a precatalyst. These methodologies provide a novel route to partially functionalized aryl fluorides, which have potential utility as building blocks for the synthe-