Functionalization of octaspherosilicate (HSiMe2O)8Si8O12 with buta-1,3-diynes by hydrosilylation

Abstract

AbstractHydrosilylation with octaspherosilicate (HSiMe2O)8Si8O12 (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, SiR3), making them highly desirable, giant building blocks in organic synthesis and material chemistry. These compounds were fully characterized by 1H, 13C, 29Si, 1D NOE, 1H–13C HSQC NMR, FT–IR, and MALDI TOF MS, EA, UV–Vis, and TGA analysis. The TGA proved their high thermal stability up to 427 ℃ (Td10%) for compound 3j.