Stefanowska Kinga, Franczyk Adrian, Szyling Jakub, Pyziak Mikołaj, Pawluć Piotr, Walkowiak Jędrzej
Centre for Advanced Technologies, Adam Mickiewicz University in Poznan, Umultowska 89c, 61-614, Poznan, Poland.
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, 61-614, Poznan, Poland.
Chem Asian J. 2018 Jun 6. doi: 10.1002/asia.201800726.
Comprehensive studies on platinum-catalyzed hydrosilylation of a wide range of terminal and internal alkynes with spherosilicate (HSiMe O) Si O (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 ( H, C, Si NMR, FTIR, MALDI TOF or TOF MS ES analysis). Moreover, the molecular structure of the compound (Me Si(H)C=C(H)SiMe O) Si O (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.
对球硅石（HSiMeO）SiO（1a）与多种端炔和内炔进行铂催化硅氢化反应的综合研究。详细研究了反应参数、试剂和催化剂类型对该过程效率的影响，该过程能够创建一种通用且选择性的方法来合成烯烃八官能化八球硅石。在这项工作中，以高产率选择性地获得了二十种新型的1,2-（E）-二取代和1,1,2-（E）-三取代烯基八球硅石（3a-m，6n-t），并进行了全面表征（1H、13C、29Si 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（MeSi（H）C=C（H）SiMeO）SiO（3a）的分子结构。所开发的方法首次允许1a与端硅基、锗基、芳基和烷基炔进行选择性硅氢化反应，以及通过内炔的硅氢化反应将十六个官能团直接引入1a结构中。该方法是合成具有Si-O基立方核的超支化化合物的有力工具。所得产物由于其独特的结构和物理化学性质，被认为是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的新型、多功能、杂化和纳米级构建块。在本合成中使用了市售试剂和催化剂，因此这些方法可以很容易地重复、快速放大并广泛应用。
