Activation of aryl chlorides for Suzuki cross-coupling by ligandless, heterogeneous palladium

[GRAPHICS] We demonstrate that Pd/C without added ligands catalyzes the Suzuki cross-coupling reaction with aryl chlorides. The ability of heterogeneous Pd to activate the C-CI bond is explained in terms of a synergistic anchimeric and electronic effect that occurs between the Pd surface and the aryl chloride. Furthermore, the importance of selectivity control following C-CI bond activation is illustrated by the striking role that solvents play in determining homo- vs cross coupling pathways of the aryl chlorides.