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Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol
Authors:Dr Shintaro Ishida  Dr Takashi Abe  Dr Fumiya Hirakawa  Tomoyuki Kosai  Katsuhiro Sato  Prof?Dr Mitsuo Kira  Prof?Dr Takeaki Iwamoto
Institution:Department of Chemistry, Graduate School of Science, Tohoku University, Aoba‐ku, Sendai 980‐8578 (Japan)
Abstract:A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In 29Si NMR spectrum in D8]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a 2+3] cycloadduct, respectively. The silanone remains intact in D8]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures.
Keywords:cycloaddition  ketones  multiple bonds  silanone
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