P‑Chiral Phosphine–Sulfonate/Palladium-Catalyzed Asymmetric Copolymerization of Vinyl Acetate with Carbon Monoxide

Utilization of palladium catalysts bearing a P-chiral phosphine–sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination–insertion (co)­polymerization of vinyl acetate.