Cobalt-Catalyzed Regiodivergent Double Hydrosilylation of Arylacetylenes |
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Authors: | Dr Zhaoyang Cheng Minghua Li Xu-Yang Zhang Yue Sun Qing-Lei Yu Prof Dr Xing-Hong Zhang Prof Dr Zhan Lu |
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Institution: | 1. Department of Chemistry, Zhejiang University, Hangzhou, 310058 China
These authors contributed equally to this work.;2. Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027 China;3. Department of Chemistry, Zhejiang University, Hangzhou, 310058 China |
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Abstract: | Double hydrosilylation of alkynes represents a straightforward method to synthesize bis(silane)s, yet it is challenging if α-substituted vinylsilanes act as the intermediates. Here, a cobalt-catalyzed regiodivergent double hydrosilylation of arylacetylenes is reported for the first time involving this challenge, accessing both vicinal and geminal bis(silane)s with exclusive regioselectivity. Various novel bis(silane)s containing Si−H bonds can be easily obtained. The gram-scale reactions could be performed smoothly. Preliminarily mechanistic studies demonstrated that the reactions were initiated by cobalt-catalyzed α-hydrosilylation of alkynes, followed by cobalt-catalyzed β-hydrosilylation of the α-vinylsilanes to deliver vicinal bis(silane)s, or hydride-catalyzed α-hydrosilylation to give geminal ones. Notably, these bis(silane)s can be used for the synthesis of high-refractive-index polymers (nd up to 1.83), demonstrating great potential utility in optical materials. |
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Keywords: | Alkyne Cobalt Dihydrosilylation Polymer Regiodivergent |
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