This article reviews the advances made over the past five decades of research in developing effective chemocatalytic pathways to synthesize polyhydroxyalkanoates (PHAs), a prominent class of biodegradable polyesters found in nature and considered as sustainable alternatives to petroleum-based non-degradable plastics. Focused in this review are recent efforts that seek to address the key challenges facing the biosynthetic routes by taking advantage of precision in synthesis, expedient tunability in polymer stereomicrostructures and structures of monomers and molecular catalysts, as well as scalability and speed in polymer production that chemical catalysis can offer. This article is organized by poly(3-hydroxybutyrate) (P3HB) stereomicrostructures (tacticities), from isotactic to syndiotactic to atactic P3HB materials, followed by other PHA homopolymers and copolymers. Under each type of stereochemically defined PHAs, monomers, catalysts, and polymerizations employed for the synthesis, as well as mechanistic aspects when possible, are described. Next, recent advances in expanding the PHA scope and developing functionalized, uncommon or unnatural PHAs, inaccessible by biological methods, especially block and stereoblock or stereosequenced PHAs, are highlighted in their synthetic methods and advanced materials properties. Lastly, four key remaining challenges, and thus corresponding future directions directed at addressing those challenges, are discussed.

本文回顾了过去 5 年在开发合成聚羟基链烷酸酯 (PHA) 的有效化学催化途径方面取得的进展，PHA 是自然界中发现的一类突出的可生物降解聚酯，被认为是石油基不可降解塑料的可持续替代品。本综述的重点是最近的努力，旨在通过利用合成的精确性、聚合物立体微观结构和单体和分子催化剂结构的便捷可调性以及聚合物生产的可扩展性和速度来解决生物合成路线面临的关键挑战。催化可以提供。本文由聚 (3-羟基丁酸酯) (P3HB) 立体微观结构（立构规整度）整理，从等规到间规再到无规 P3HB 材料，其次是其他 PHA 均聚物和共聚物。在每种类型的立体化学定义的 PHA 下，描述了用于合成的单体、催化剂和聚合，以及可能的机理方面。接下来，在扩大 PHA 范围和开发功能化、不常见或非天然 PHA 方面的最新进展，这些 PHA 无法通过生物学方法获得，尤其是嵌段和立体嵌段或立体测序的 PHA，在其合成方法和先进材料特性方面得到了强调。最后，讨论了四个关键的剩余挑战，以及解决这些挑战的相应未来方向。在扩大 PHA 范围和开发功能化、不常见或非天然 PHA 方面的最新进展，这些 PHA 无法通过生物学方法获得，尤其是嵌段和立体嵌段或立体测序的 PHA，其合成方法和先进的材料特性突出显示。最后，讨论了四个关键的剩余挑战，以及解决这些挑战的相应未来方向。在扩大 PHA 范围和开发功能化、不常见或非天然 PHA 方面的最新进展，这些 PHA 无法通过生物学方法获得，尤其是嵌段和立体嵌段或立体测序的 PHA，其合成方法和先进的材料特性突出显示。最后，讨论了四个关键的剩余挑战，以及解决这些挑战的相应未来方向。