Access to Polyhydroxyalkanoates with Diverse Syndiotacticity via Polymerization by Spiro‐Salen Complexes and Insights into the Stereocontrol Mechanism

Abstract Polyhydroxyalkanoates (PHAs) have attracted broad interest as promising sustainable materials to address plastic pollution and resource scarcity. However, the chemical synthesis of stereoregular PHAs via ring‐opening polymerization (ROP) has long been an elusive endeavor. In this contribution, we exploited a robust spiro‐salen yttrium complex ( Y3 ) as the catalyst to successfully prepare syndiotactic PHAs with diverse pendent groups. Simply altering the ratio of enantiomeric catalysts allowed to access of PHAs with diverse syndiotacticity ( P r =0.5–0.99, from sticky oil to tough materials), delivering tunable thermal properties (glass transition temperature, T g from −52 to 70 °C and melting transition temperature, T m from 38 to 223 °C). A combined experimental and computational study suggested a polymeric exchange mechanism could boost the polymerization activity and control the syndioselectivity.