Harnessing the β-boron effect for regioselective Ru-catalyzed hydrosilylation of internal alkynes

作者：Jiasheng Qian, Shuang Lin, Zhihao Chen, Jiawu Huang, Wenjin Zhang, Qingjiang Li, Tian‐Yu Sun, Honggen Wang · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-59823-x · 被引用次数：4 · 研究领域：Organoboron and organosilicon chemistry、Catalytic C–H Functionalization Methods、Catalytic Cross-Coupling Reactions

Metal-catalyzed hydrosilylation of alkynes is recognized as a straightforward and atom economic method for synthesizing alkenylsilanes. While substantial advancements have been made with terminal alkynes, achieving precise regio- and stereocontrol with unsymmetrical internal alkynes remains a significant challenge. In this study, we report the utilization of an intriguing β-boron effect in metal catalysis, enabling an exclusively regioselective Ru-catalyzed hydrosilylation of propargylic N-methyliminodiacetic acid boronates (B(MIDA)) to synthesize alkenylsilanes. Variations in the Ru catalyst can lead to stereo-divergency without compromising regioselectivity. Density functional theory (DFT) calculations indicate that the hyperconjugative effect of the σ(C-B) bond, which stabilizes the electrophilic metallacyclopropene intermediate with Fischer carbene character, is crucial for achieving high regioselectivity. The observed switch in stereoselectivity is attributed to the different steric effects of 1,2,3,4,5-pentamethylcyclopenta-1,3-diene (Cp*) and cyclopenta-1,3-diene (Cp) ligands in the catalyst. This method produces a diverse array of regio- and stereodefined products incorporating boryl, silyl, and alkene functionalities, each of which serves as a valuable handle for further functionalization.