Functionalized Cyclic Poly(α‐Hydroxy Acids) via Controlled Ring‐Opening Polymerization of O‐Carboxyanhydrides

Abstract Linear poly(α‐hydroxy acids) are important degradable polymers, and they can be efficiently prepared by ring‐opening polymerization of O‐carboxyanhydrides with pendant functional groups. However, attempts to prepare cyclic poly(α‐hydroxy acids) have been plagued by side reactions, including epimerization and uncontrolled intramolecular chain transfers or termination, that prevent the synthesis of high‐molecular‐weight stereoregular cyclic polyesters. Herein, we report a scalable method for the synthesis of high‐molecular‐weight (>100 kDa) stereoregular functionalized cyclic poly(α‐hydroxy acids) by means of controlled polymerization of O‐carboxyanhydrides using a catalytic system consisting of a lanthanum complex with a sterically bulky ligand and a manganese silylamide. Additionally, using this system, we could readily prepare cyclic block poly(α‐hydroxy acids) by means of sequential addition of O‐carboxyanhydrides. The obtained cyclic polyesters and their cyclic block copolyesters exhibit distinctive physicochemical properties—including elevated phase transition temperature, improved toughness, and reduced viscosity—compared to their linear counterparts.