Disiloxane Synthesis Based on Silicon–Hydrogen Bond Activation using Gold and Platinum on Carbon in Water or Heavy Water

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• 作者：Yoshinari Sawama ; Masahiro Masuda ; Naoki Yasukawa ; Ryosuke Nakatani ; Shumma Nishimura ; Kyoshiro Shibata ; Tsuyoshi Yamada ; Yasunari Monguchi ; Hiroyasu Suzuka ; Yukio Takagi ; Hironao Sajiki
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：May 20, 2016
• 年：2016
• 卷：81
• 期：10
• 页码：4190-4195
• 全文大小：423K
• 年卷期：0
• ISSN：1520-6904

文摘

Disiloxanes possessing a silicon–oxygen linkage are important as frameworks for functional materials and coupling partners for Hiyama-type cross coupling. We found that disiloxanes were effectively constructed of hydrosilanes catalyzed by gold on carbon in water as the solvent and oxidant in association with the emission of hydrogen gas at room temperature. The present oxidation could proceed via various reaction pathways, such as the hydration of hydrosilane into silanol, dehydrogenative coupling of hydrosilane into disilane, and the subsequent corresponding reactions to disiloxane. Additionally, the platinum on carbon catalyzed hydrogen–deuterium exchange reaction of arylhydrosilanes as substrates in heavy water proceeded on the aromatic nuclei at 80 °C with high deuterium efficiency and high regioselectivity at the only meta and para positions of the aromatic–silicon bond to give the deuterium-labeled disiloxanes.