通过硅氢化反应使八聚硅氧烷（HSiMeO）SiO与1,3 - 丁二炔官能化。

Functionalization of octaspherosilicate (HSiMeO)SiO with buta-1,3-diynes by hydrosilylation.

作者信息

Stefanowska Kinga, Nagórny Jakub, Szyling Jakub, Franczyk Adrian

机构信息

Center for Advanced Technology, Adam Mickiewicz University, Uniwersytetu Poznanskiego 10, 61-614, Poznan, Poland.

Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, 61-614, Poznan, Poland.

出版信息

Sci Rep. 2023 Aug 31;13(1):14314. doi: 10.1038/s41598-023-41461-2.

DOI:10.1038/s41598-023-41461-2

PMID:37653063

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10471723/

Abstract

Hydrosilylation with octaspherosilicate (HSiMeO)SiO (1) has provided hundreds of molecular and macromolecular systems so far, making this method the most popular in the synthesis of siloxane-based, nanometric, cubic, and reactive building blocks. However, there are no reports on its selective reaction with 1,3-diynes, which allows for the formation of new products with unique properties. Therefore, herein we present an efficient protocol for monohydrosilylation of symmetrically and non-symmetrically 1,4-disubstituted buta-1,3-diynes with 1. The compounds obtained bear double and triple bonds and other functionalities (e.g., Br, F, OH, SiR), making them highly desirable, giant building blocks in organic synthesis and material chemistry. These compounds were fully characterized by H, C, Si, 1D NOE, H-C HSQC NMR, FT-IR, and MALDI TOF MS, EA, UV-Vis, and TGA analysis. The TGA proved their high thermal stability up to 427 ℃ (T) for compound 3j.

摘要

到目前为止，使用八球硅石（HSiMeO）SiO（1）进行硅氢化反应已得到了数百种分子和大分子体系，使得该方法成为合成硅氧烷基、纳米级、立方体型和反应性结构单元中最常用的方法。然而，尚无关于其与1,3 - 二炔选择性反应的报道，而这种反应能够生成具有独特性质的新产品。因此，本文我们提出了一种使用1对对称和非对称1,4 - 二取代丁二炔 - 1,3 - 二炔进行单硅氢化反应的有效方案。所得到的化合物含有双键和三键以及其他官能团（如Br、F、OH、SiR），使其成为有机合成和材料化学中非常理想的大型结构单元。这些化合物通过H、C、Si、1D NOE、H - C HSQC NMR、FT - IR以及MALDI TOF MS、EA、UV - Vis和TGA分析进行了全面表征。TGA证明化合物3j在高达427℃（T）时具有高热稳定性。