Catalytic ipso-Nitration of Organosilanes Enabled by Electrophilic N-Nitrosaccharin Reagent |
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| Authors: | Ivan Mosiagin Dr Anthony J Fernandes Alena Budinská Liana Hayriyan Prof Dr Kai E O Ylijoki Prof Dr Dmitry Katayev |
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| Institution: | 1. Department of Chemistry, University of Fribourg, Chemin du Musée 9, 1700 Fribourg, Switzerland;2. Department of Chemistry, Biochemistry, and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland;3. Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland;4. Department of Chemistry, Saint Mary's University, 923 Robie Street, Halifax, NS B3H 3 C3 Canada |
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| Abstract: | Nitroaromatic compounds represent one of the essential classes of molecules that are widely used as feedstock for the synthesis of intermediates, the preparation of nitro-derived pharmaceuticals, agrochemicals, and materials on both laboratory and industrial scales. We herein disclose the efficient, mild, and catalytic ipso-nitration of organotrimethylsilanes, enabled by an electrophilic N-nitrosaccharin reagent and allows chemoselective nitration under mild reaction conditions, while exhibiting remarkable substrate generality and functional group compatibility. Additionally, the reaction conditions proved to be orthogonal to other common functionalities, allowing programming of molecular complexity via successive transformations or late-stage nitration. Detailed mechanistic investigation by experimental and computational approaches strongly supported a classical electrophilic aromatic substitution (SEAr) mechanism, which was found to proceed through a highly ordered transition state. |
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| Keywords: | Electrophilic Ipso-Substitution Nitration Organosilanes Selectivity |
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