Abstract
Palladium-catalyzed alternating copolymerization of olefins with carbon monoxide has been successfully applied to new substrates, namely, 3-perfluoroalkyl-substituted 1-propene (1) and vinyl acetate. The key to success was the choice of ligands. The bulky phosphine-phosphite ligand, (R, S) -BINAPHOS (2e) realized the 1, 2-insertion of 1a, b to enable the subsequent CO insertion. With phosphine-sulfonate ligand 7a, the first example of the alternating copolymerization of vinyl acetate with CO has been performed via CO insertion to the stable chelation intermediate which has never been performed with the conventional ligands for the copolymerization.
