Organometallic Chemistry Laboratory, RIKEN , 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science , 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
J Am Chem Soc. 2017 Sep 13;139(36):12434-12437. doi: 10.1021/jacs.7b08053. Epub 2017 Aug 31.
The substituent redistribution of hydrosilanes on silicon through C-Si and Si-H bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective C-Si/Si-H bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(CF). This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes.
通过 C-Si 和 Si-H 键的断裂和重组,硅氢烷在硅上的取代基重排具有重要意义,但这种转化通常难以以选择性的方式实现。通过使用富电子的芳基硅烷,我们首次在硼催化剂 B(CF)的存在下实现了一系列硅烷的选择性 C-Si/Si-H 键同系交叉复分解。该方法具有反应条件简单、化学选择性高、底物范围广、官能团容忍度高的特点,为多取代官能化硅烷的合成提供了新途径。