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Harnessing the β-boron effect for regioselective Ru-catalyzed hydrosilylation of internal alkynes
Jiasheng Qian1, Shuang Lin1, Zhi-Hao Chen1
1State Key Laboratory of Anti-Infective Drug Discovery and Development, Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou, China.
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.
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