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

A. Nakamura, T. Kageyama, H. Goto, B. P. Carrow, S. Ito, K. Nozaki*
J. Am. Chem. Soc. 2012, 134, 12366–12369.  DOI: 10.1021/ja3044344

Abstract: 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.

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