ArticleNature communications2025
Harnessing the β-boron effect for regioselective Ru-catalyzed hydrosilylation of internal alkynes.
Article in Nature communications, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 1 paper.
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1 citing paper in PubMed.
- Enantioselective Synthesis of Atropisomeric 1,3-Dienes via Platinum-Catalyzed Hydrosilylation of 1,3-Enynes.Angewandte Chemie (International ed. in English) · 2026Article
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Authors and funding
8 authors.
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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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