Sensibility to environmental concerns and the actual demand for polymeric materials free of any metal contaminants in most applications have directed research towards significant breakthroughs in organocatalytic polymerizations. The overarching challenge is to develop new and efficient organocatalysts for extending the scope and to improve the performance of organocatalytic polymerizations. Since 2016 commercially available alkyl boranes, especially triethyl borane (TEB), have been discovered as exceptional Lewis acids that served to generate ate complexes by combination with chain ends on the one hand and to activate epoxides on the other. This double role of boranes has received widespread attention especially in oxygenated polymer synthesis. Lewis pairs consisting of alkyl boranes combined with an onium salt or organic base has indeed demonstrated unprecedented versatility for (co)polymerizations of oxygenated monomers such as epoxides, oxetanes, cyclic esters and with CO₂, COS, isocyanates, or cyclic anhydrides, producing a variety of oxygenated polymers. In this review, we take TEB-mediated polymerization systems as the main line of emerging area, summarize the progress comprehensively made to promote the rapid development of organocatalytic polymerizations of oxygenated polymers by these systems, and propose key challenges in organocatalytic synthesis in the future.

在大多数应用中，对环境问题的敏感性和对不含任何金属污染物的聚合物材料的实际需求已将研究导向有机催化聚合的重大突破。首要的挑战是开发新的高效有机催化剂以扩大范围并提高有机催化聚合的性能。自 2016 年以来，市售的烷基硼烷，尤其是三乙基硼烷 (TEB)，被发现是一种特殊的路易斯酸，可用于产生酸一方面通过与链端结合形成复合物，另一方面激活环氧化物。硼烷的这种双重作用受到广泛关注，尤其是在含氧聚合物合成中。由烷基硼烷与鎓盐或有机碱组成的路易斯对确实证明了含氧单体（如环氧化物、氧杂环丁烷、环酯）和与 CO _{2的（共）聚合的前所未有的多功能性}、COS、异氰酸酯或环酐，生成多种含氧聚合物。在这篇综述中，我们以TEB介导的聚合体系作为新兴领域的主线，全面总结了这些体系为促进含氧聚合物有机催化聚合的快速发展所取得的进展，并提出了未来有机催化合成的关键挑战。