Iron-Catalyzed Stereoconvergent 1,4-Hydrosilylation of Conjugated Dienes |
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Authors: | Wei Sun Dr. Meng-Yang Hu Zhan-Sheng Lu Dr. Ming-Yao Huang Xin-Yu Zhang Prof. Dr. Shou-Fei Zhu |
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Affiliation: | Frontiers Science Center for New Organic Matter, State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071 China |
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Abstract: | Stereoconvergent transformation of E/Z mixtures of olefins to products with a single steric configuration is of great practical importance but hard to achieve. Herein, we report an iron-catalyzed stereoconvergent 1,4-hydrosilylation reactions of E/Z mixtures of readily available conjugated dienes for the synthesis of Z-allylsilanes with high regioselectivity and exclusive stereoselectivity. Mechanistic studies suggest that the reactions most likely proceed through a two-electron redox mechanism. The stereoselectivity of the reactions is ultimately determined by the crowded reaction cavity of the α-diimine ligand-modified iron catalyst, which forces the conjugated diene to coordinate with the iron center in a cis conformation, which in turn results in generation of an anti-π-allyl iron intermediate. The mechanism of this stereoconvergent transformation differs from previously reported mechanisms of other related reactions involving radicals or metal-hydride species. |
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Keywords: | Allylsilanes Conjugated Dienes Hydrosilylation Reactions Iron Catalysis Stereoconvergent Transformations |
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