Wang Xiao-Qing, Zhai Xiao-Yong, Wu Bo, Bai Yu-Qing, Zhou Yong-Gui
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
University of Chinese Academy of Sciences, Beijing 100049, People's Republic of China.
ACS Macro Lett. 2020 Jul 21;9(7):969-973. doi: 10.1021/acsmacrolett.0c00225. Epub 2020 Jun 16.
The precise synthesis of chiral poly(silyl ether)s remains a challenge, in contrast to the well-studied preparation of poly(silyl ether)s. Herein, an unprecedented approach for the synthesis of optically active poly(silyl ether)s with main-chain chirality has been developed via CuH-catalyzed hydrosilylation polymerization of diketones and silanes. The polymerization features low catalyst loading, mild condition, and broad substrate scope, including a wide range of aromatic diketones and heteroaromatic diketones with excellent yields and enantioselectivities (up to 98% yield and 99% ee). Thermal analysis indicated chiral poly(silyl ether)s exhibit good thermal properties. These enantiomerically enriched poly(silyl ether)s with good thermal stability have a promising application in chiral separation.
与已得到充分研究的聚（硅醚）制备方法相比，手性聚（硅醚）的精确合成仍然是一个挑战。在此，通过铜氢催化的二酮与硅烷的硅氢化聚合反应，开发出了一种前所未有的合成具有主链手性的光学活性聚（硅醚）的方法。该聚合反应具有催化剂负载量低、条件温和以及底物范围广的特点，包括多种芳香族二酮和杂芳香族二酮，产率和对映选择性都很高（产率高达98%，对映体过量值高达99%）。热分析表明手性聚（硅醚）具有良好的热性能。这些具有良好热稳定性的对映体富集聚（硅醚）在手性分离方面有着广阔的应用前景。
