Tug‐of‐War between Two Distinct Catalytic Sites Enables Fast and Selective Ring‐Opening Copolymerizations

Ring-opening copolymerizations have emerged as a powerful approach towards the creation of sustainable polymers. Typical H-bonding catalysts for ring-opening are subject to a single catalytic site. Here we describe a H-bond-donor/Lewis-acidic-boron organocatalyst featuring two distinct catalytic sites in one molecule. The ring-opening copolymerization of epoxides with anhydride mediated by these modular, and tunable catalysts achieves high selectivity (>99 % polyester selectivity) and markedly higher activity compared to either of the di-thiourea analogues or any combinations of them. Calculations and experimental studies reveal that the superior catalytic performance arises from tug-of-war between two differentiated catalytic sites: thiourea pulls off the propagating chain-end from boron center, simultaneously enhancing the role of monomer activation and also nucleophilicity of the propagation intermediates.