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Anti-Markovnikov hydrosilylation and Markovnikov hydroboration of alkenes by a phenanthroline-based tridentate manganese catalyst
Journal of Catalysis ( IF 6.5 ) Pub Date : 2023-11-05 , DOI: 10.1016/j.jcat.2023.115197
Ming Huang , Xiaoyu Zhou , Youxiang Shao , Yinwu Li , Yan Liu , Zhuofeng Ke

The divergent regioselective hydrosilylation and hydroboration of alkenes by a single manganese catalyst are disclosed. Using the Mn catalyst bearing the tridentate phenanthroline scaffold, alkenes were found to undergo anti-Markovnikov hydrosilylation, while the hydroboration of alkenes afforded Markovnikov's products. Both the hydrosilylation and the hydroboration of alkenes proceed under mild conditions (room temperature, neat conditions) with low catalyst loadings (1 mol%) using NaOtBu (3 mol%) as an activator. The reactions are atom-economical, exhibiting a broad substrate scope (46 examples), and excellent functional group tolerance (including aromatic and aliphatic alkenes). Importantly, the presented catalytic systems are suitable for various synthetic applications, and could be extended to the synthesis of bioactive molecules. Mechanistic studies supported that the Mn-H species are crucially important for the catalytic process.



中文翻译:

基于菲咯啉的三齿锰催化剂对烯烃的反马尔科夫尼科夫氢化硅烷化和马尔科夫尼科夫硼氢化反应

公开了通过单一锰催化剂进行烯烃的不同区域选择性氢化硅烷化和硼氢化反应。使用带有三齿菲咯啉骨架的锰催化剂,发现烯烃发生反马可夫尼科夫氢化硅烷化,而烯烃的硼氢化作用提供了马可夫尼科夫产物。烯烃的氢化硅烷化和硼氢化反应均在温和条件(室温、纯净条件)下以低催化剂负载量 (1 mol%) 使用 NaO t Bu (3 mol%) 作为活化剂进行。该反应具有原子经济性,具有广泛的底物范围(46 个实例)和出色的官能团耐受性(包括芳香族和脂肪族烯烃)。重要的是,所提出的催化系统适用于各种合成应用,并且可以扩展到生物活性分子的合成。机理研究表明 Mn-H 物质对于催化过程至关重要。

更新日期:2023-11-05
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