Affiliation:
1. National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan) College of Chemistry Sichuan University 29 Wangjiang Rd Chengdu 610064 P. R. China
2. Key Laboratory of Green Chemistry and Technology of Ministry of Education College of Chemistry Sichuan University Chengdu 610064 P. R. China
Abstract
AbstractIsotactic polythioesters (PTEs) that are thioester analogs to natural polyhydroxyalkanoates (PHAs) have attracted growing attention due to their distinct properties. However, the development of chemically synthetic methods for preparing isotactic PTEs has long been an intricate endeavour. Herein, we report the successful synthesis of perfectly isotactic PTEs via stereocontrolled ring‐opening polymerization. This binaphthalene‐salen aluminium (SalBinam‐Al) catalyst promoted a robust polymerization of rac‐α‐substituted‐β‐propiothiolactones (rac‐BTL and rac‐PTL) with highly kinetic resolution, affording perfectly isotactic P(BTL) and P(PTL) with Mn up to 276 kDa. Impressively, the isotactic P(BTL) formed a supramolecular stereocomplex with improved thermal property (Tm=204 °C). Ultimately, this kinetic resolution polymerization enabled the facile isolation of enantiopure (S)‐BTL, which could efficiently convert to an important pharmaceutical building block (S)‐2‐benzyl‐3‐mercapto‐propanoic acid. Isotactic P(PTL) served as a tough and ductile material comparable to the commercialized polyolefins. This synthetic system allowed to access of isotactic PTEs, establishing a powerful platform for the discovery of sustainable plastics.
Funder
National Key Research and Development Program of China
National Natural Science Foundation of China