Synthesis of Functionalized (Poly)Siloxanes via Iron-Catalyzed C–H Bond Alkylation with Polar Olefins
Rong Zeng , Chengxiang Zhou , Zuguang Yang , Weiping Liu , Sichang Wang , Congyu Ke
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (24) : 3489 -3495.
The synthesis of functionalized linear polysiloxanes has garnered considerable attentions due to their broad applicability. While the selective C−H bond functionalization of dimethylsiloxane monomers or polymers offers a promising and versatile approach, it remains a significant synthetic challenge. In this study, we report a mild and efficient iron-catalyzed method for the C−H bond alkylation of both dimethylsiloxane monomers and polysiloxane using polar alkenes as coupling partners. This protocol exhibits broad substrate scope, tolerating a wide range of siloxane/silane substrates and polar alkenes. A variety of functional groups, including amide, ester, ketone, and nitrile, can be readily introduced into the siloxane framework. Functionalized polysiloxanes are accessible either through direct C−H bond functionalization or via copolymerization using the modified monomers. Notably, nitrile-functionalized polysiloxanes display significant photoluminescence properties, offering new opportunities for expanding the application scope of polysiloxane materials. Based on experimental studies, a plausible catalytic mechanism is also proposed.
Functionalized siloxane / Iron catalysis / C−H functionalization / Polysiloxane
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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