Isotactic 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.

中文翻译：

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动态拆分聚合实现完美全同立构聚硫酯的化学合成

全同立构聚硫酯（PTE）是天然聚羟基脂肪酸酯（PHA）的硫酯类似物，由于其独特的性质而引起了越来越多的关注。然而，开发制备全同立构 PTE 的化学合成方法长期以来一直是一项复杂的工作。在此，我们报告了通过立体控制开环聚合成功合成了完全全同立构的 PTE。这种联萘-salen铝（SalBinam-Al）催化剂以高动力学分辨率促进了rac-α-取代-β-丙硫内酯（rac-BTL和rac-PTL）的稳健聚合，提供了完美的全同立构P（BTL）和P（PTL） ），Mn 高达 276 kDa。令人印象深刻的是，全同立构的 P(BTL) 形成了具有改善的热性能（Tm = 204 °C）的超分子立体复合物。最终，这种动力学拆分聚合能够轻松分离对映体纯 (S)-BTL，它可以有效地转化为重要的药物结构单元 (S)-2-苄基-3-巯基-丙酸。全同立构 P(PTL) 是一种与商业化聚烯烃相当的坚韧和延展性材料。该合成系统允许获得等规 PTE，为发现可持续塑料建立了强大的平台。