Selective Hydrosilylation of Alkynes with Octaspherosilicate (HSiMe2O)8Si8O12,Chemistry - An Asian Journal

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Selective Hydrosilylation of Alkynes with Octaspherosilicate (HSiMe2O)8Si8O12
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-07-18 , DOI: 10.1002/asia.201800726
Kinga Stefanowska _{1,

2} , Adrian Franczyk ₁ , Jakub Szyling _{1,

2} , Mikołaj Pyziak ₂ , Piotr Pawluć _{1,

2} , Jędrzej Walkowiak ₁

Affiliation

Comprehensive studies on platinum‐catalyzed hydrosilylation of a wide range of terminal and internal alkynes with spherosilicate (HSiMe₂O)₈Si₈O₁₂ (1 a) were performed. The influence of the reaction parameters and the types of reagents and catalysts on the efficiency of the process, which enabled the creation of a versatile and selective method to synthesize olefin octafunctionalized octaspherosilicates, was studied in detail. Within this work, twenty novel 1,2‐(E)‐disubstituted and 1,1,2‐(E)‐trisubstituted alkenyl‐octaspherosilicates (3 a–m, 6 n–t) were selectively obtained with high yields, and fully characterized (¹H, ¹³C, ²⁹Si NMR, FTIR, MALDI TOF or TOF MS ES⁺ analysis). Moreover, the molecular structure of the compound (Me₃Si(H)C=C(H)SiMe₂O)₈Si₈O₁₂ (3 a) was determined by X‐ray crystallography for the first time. The developed procedures are the first that allow selective hydrosilylation of terminal silyl, germyl, aryl, and alkyl alkynes with 1 a, as well as the direct introduction of sixteen functional groups into the 1 a structure by the hydrosilylation of internal alkynes. This method constituted a powerful tool for the synthesis of hyperbranched compounds with a Si−O based cubic core. The resulting products, owing to their unique structure and physicochemical properties, are considered novel, multifunctional, hybrid, and nanometric building blocks, intended for the synthesis of star‐shaped molecules or macromolecules, as well as nanofillers and polymer modifiers. In the presented syntheses, commercially available reagents and catalysts were used, so these methods can be easily repeated, rapidly scaled up, and widely applied.

中文翻译：

炔烃与八球硅酸盐 (HSiMe2O)8Si8O12 的选择性氢化硅烷化

对铂催化的多种末端和内部炔烃与球硅酸盐 (HSiMe ₂ O) ₈ Si ₈ O ₁₂ ( 1 a ) 的硅氢加成进行了全面研究。详细研究了反应参数以及试剂和催化剂类型对工艺效率的影响，从而创建了一种合成烯烃八官能化八球硅酸酯的通用且选择性的方法。在这项工作中，选择性地以高产率获得了 20 种新型 1,2-( E )-二取代和 1,1,2-( E )-三取代烯基八球硅酸盐 ( 3 a – m , 6 n – t )，并且完全表征（ ¹ H、 ¹³ C、 ²⁹ Si NMR、FTIR、MALDI TOF 或 TOF MS ES ⁺分析）。此外，首次通过X射线晶体学确定了化合物(Me ₃ Si(H)C=C(H)SiMe ₂ O) ₈ Si ₈ O ₁₂ ( 3a )的分子结构。所开发的程序是第一个允许末端甲硅烷基、甲锗烷基、芳基和烷基炔与1a选择性氢化硅烷化，以及通过内部炔烃的氢化硅烷化将16个官能团直接引入1a结构中的程序。该方法构成了合成具有 Si−O 立方核的超支化化合物的强大工具。由此产生的产品，由于其独特的结构和物理化学性质，被认为是新颖的、多功能的、混合的和纳米结构单元，用于合成星形分子或大分子，以及纳米填料和聚合物改性剂。在所提出的合成中，使用了市售试剂和催化剂，因此这些方法可以轻松重复、快速扩大规模并广泛应用。

更新日期：2018-07-18

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