Ultrarapid Cerium(III)–NHC Catalysts for High Molar Mass Cyclic Polylactide

Cyclic polyesters could improve the properties of degradable plastics, but routes to them that provide a product with faster rates, higher molar mass, and greater selectivity for cyclic vs linear polymer are needed. Here, homogeneous Ce­(III)–N-heterocyclic carbene (NHC) catalysts show outstanding activities (turn-over-frequency (TOF) > 864 000 h–1), excellent control, and selectivity for cyclic polylactide (PLA) topology (>95%), yielding high molar mass PLA (60 Mn –1). They efficiently produce cyclic PLA from rac-lactide or l-lactide and aliphatic cyclic polyesters from ε-caprolactone or β-butyrolactone. The enhanced performances are only achievable from combining cooperative Lewis acidic cerium­(III) and hemilabile N-heterocyclic carbene functionalities.