Abstract As a kind of material possessing thermal stability, biocompatibility and degradability, polysilylethers (PSEs) have potential applications. Different catalytic systems have been developed for the synthesis of PSEs. However, the resulted PSEs have similar structure, which is unfavorable for adjusting its properties. We herein synthesized a series of novel PSEs with pendant Si H groups via cobalt-catalyzed selective dehydrocoupling polymerization. Various diols and prochiral silanes are suitable for this method. This novel PSEs could also be obtained via a Co-catalyzed one-pot two-step process. Furthermore, asymmetric dehydrocoupling polymerization was studied and high-Mn PSE was obtained. After the cleavage of PSE by methyl magnesium iodide, chiral silane was obtained with high yield and moderate enantioselectivity.

中文翻译：

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钴催化前手性硅烷和二醇的选择性脱氢偶联聚合

摘要 作为一种具有热稳定性、生物相容性和可降解性的材料，聚甲硅烷基醚（PSEs）具有潜在的应用前景。已经开发了不同的催化系统来合成 PSE。然而，所得PSEs具有相似的结构，不利于调整其性能。我们在此通过钴催化的选择性脱氢偶联聚合合成了一系列具有侧链 Si H 基团的新型 PSE。各种二醇和前手性硅烷适用于该方法。这种新型 PSE 也可以通过共催化的一锅两步法获得。此外，还研究了不对称脱氢偶联聚合，并获得了高锰 PSE。PSE被甲基碘化镁裂解后，得到高产率和中等对映选择性的手性硅烷。