Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China.
School of Materials Science and Engineering, PCFM Lab, Sun Yat-sen University, Guangzhou, China.
Nat Commun. 2021 Jun 3;12(1):3304. doi: 10.1038/s41467-021-23326-2.
Sila-molecules have recently attracted attention due to their promising applications in medical and industrial fields. Compared with all-carbon parent compounds, the different covalent radius and electronegativity of silicon from carbon generally endow the corresponding sila-analogs with unique biological activity and physicochemical properties. Vinylsilanes feature both silyl-hyperconjugation effect and versatile reactivities, developing vinylsilane-based Smiles rearrangement will therefore provide an efficient platform to assemble complex silacycles. Here we report a practical Ir(III)-catalyzed cycloaromatization of ortho-alkynylaryl vinylsilanes with arylsulfonyl azides for delivering naphthyl-fused benzosiloles under visible-light photoredox conditions. The combination of experiments and density functional theory (DFT) energy profiles reveals the reaction mechanism involving α-silyl radical Smiles rearrangement.
硅烯分子由于其在医学和工业领域的应用前景而受到关注。与全碳母体化合物相比，硅与碳的不同共价半径和电负性通常赋予相应的硅烷类似物独特的生物活性和物理化学性质。乙烯基硅烷具有硅烷基超共轭效应和多种反应性，因此开发基于乙烯基硅烷的 Smiles 重排将为组装复杂的硅杂环提供一个有效的平台。在这里，我们报道了一种实用的 Ir(III)催化的邻炔基芳基乙烯基硅烷与芳基磺酰叠氮化物的环芳构化反应，在可见光光还原条件下，得到萘基稠合苯并硅烷。实验和密度泛函理论（DFT）能量曲线的结合揭示了涉及α-硅基自由基 Smiles 重排的反应机理。
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