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

Jiasheng Qian, Shuang Lin, Zhi-Hao Chen, Jiawu Huang, Wenjin Zhang, Qingjiang Li, Tian-Yu Sun () and Honggen Wang ()
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Jiasheng Qian: Sun Yat-sen University
Shuang Lin: Sun Yat-sen University
Zhi-Hao Chen: Sun Yat-sen University
Jiawu Huang: Sun Yat-sen University
Wenjin Zhang: Sun Yat-sen University
Qingjiang Li: Sun Yat-sen University
Tian-Yu Sun: Peking University Shenzhen Graduate School
Honggen Wang: Sun Yat-sen University

Nature Communications, 2025, vol. 16, issue 1, 1-12

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-59823-x

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