A general, highly selective method for the room temperature Suzuki-Miyaura cross-coupling of commonly encountered primary benzamides is reported. A combination of site-selective N,N-di-Boc-activation (tert-butoxycarbonyl activation) of the amide nitrogen with practical air- and moisture-stable, well-defined, and highly reactive [Pd(NHC)(cin)Cl] (NHC = N-heterocyclic carbene; cin = cinnamyl) provides a highly effective route to biaryl ketones from primary amides in high yields. For the first time, a TON of >1000 has been achieved in amide acyl cross-coupling.