A novel Pd catalyst system, [(t-Bu)2P(OH)]2PdCl2 (POPd) with the ligand sodium 2'-(dicyclohexylphosphino)-2,6-dimethoxy-[1,1'-biphenyl]-3-sulfonate, is reported. It effectively catalyzes the Suzuki-Miyaura coupling of challenging phenyl chlorides and pyrimidinyl chlorides that are covalently linked to a double-stranded DNA-template with various boronic acids/esters.