Large-ring keto lactones having from 12 to 16 members were synthesized in fair yield by the palladium-catalyzed carbonylative coupling of long-chain esters having vinyl triflate and vinylstannane termini. A polystyrene-supported bis(diphenylphosphino)ferrocene ligand system was synthesized by the co-polymerization of styrene, p-divinylbenzene, and bis(diphenylphosphino)vinylferrocene. Palladium catalysts supported on this polymer were more selective in these carbonylative cyclizations than were corresponding homogeneous catalyst systems.