Borylated motifs hold immense potential for functional soft materials, as they can facilitate a range of reaction manifolds (e.g., analyte binding or cross-coupling). Traditional boron-containing materials are predominantly composed of either aryl boronates or main-chain embedded vinylic boronates. Progress toward expanding the architectural (and, by extension, functional) scope of borylated polymers remains slightly limited. To address this, we report the vinyl-addition polymerization of an allenylboronic acid pinacol ester. The base metal catalyst, [(η3-C₃H₅)Ni(OC(O)CF₃)]₂, was found to readily polymerize this allene monomer with good regioselectivity and molecular weight control. Additionally, the allenylboronate monomer could be copolymerized with other allenes (e.g., 1,2-nonadiene or β-pinadiene) to access an array of borylated materials. The borylated polyallenes could also be chemically tailored under mild conditions (e.g., using Pd-catalyzed cross-coupling), which suggests that they could serve as general platforms for accessing diverse architectures.

中文翻译：

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硼酸化二烯的乙烯基加成聚合反应

硼酸化基序对于功能性软材料具有巨大的潜力，因为它们可以促进一系列反应歧管（例如，分析物结合或交叉偶联）。传统的含硼材料主要由芳基硼酸酯或嵌入主链的乙烯基硼酸酯组成。在扩大硼化聚合物的结构（以及扩展功能）范围方面的进展仍然有限。为了解决这个问题，我们报告了烯基硼酸频哪醇酯的乙烯基加成聚合反应。贱金属催化剂，[(η3-C ₃ H ₅ )Ni(OC(O)CF ₃ )] ₂，发现易于聚合这种丙二烯单体，具有良好的区域选择性和分子量控制。此外，丙二烯基硼酸酯单体可以与其他丙二烯（例如 1,2-壬二烯或 β-蒎二烯）共聚以获取一系列硼化材料。硼化聚丙二烯还可以在温和条件下进行化学定制（例如，使用 Pd 催化的交叉偶联），这表明它们可以作为访问不同架构的通用平台。