Synthesis of Structurally Complex Silicon Frameworks through the First Sila-Aldol Reaction |
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Authors: | Dr Mario Leypold Lukas Schuh Prof Roland Fischer Dr Ana Torvisco Prof Michaela Flock Prof Harald Stueger Dr Michael Haas |
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Institution: | Institute of Inorganic Chemistry, Graz University of Technology, Stremayrgasse 9/IV, 8010 Graz, Austria |
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Abstract: | Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon–carbon bond-forming strategy. |
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Keywords: | carbanions charge transfer cyclic acylsilanes rearrangement cascade sila-aldol reaction |
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