Search

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. [ABSTRACT FROM AUTHOR]

Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless‐steel electrodes. The mechanism of the reaction is supported by detailed spectroscopic and experimental studies. Powered by electricity and driven by electrons, the synthetic diversity of this reaction has been demonstrated through the development of highly efficient nitration protocols of various unsaturated hydrocarbons. In addition to a broad application area, these protocols are easy to scale for decagram quantities, and exhibit exceptional substrate generality and functional‐group compatibility. [ABSTRACT FROM AUTHOR]