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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‐oxahexasilabicyclo[3.2.1]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...
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