Electron‐Driven Nitration of Unsaturated Hydrocarbons

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. Herein, we present a concept for the generation of nitryl radicals from ferric nitrate that is driven by substoichiometric amounts of electrons, introduced electrochemically. This protocol enables access to a variety of nitro‐derived molecules from unsaturated hydrocarbons including alkenes, alkynes, and arenes, in addition to promoting ipso‐nitration reactions and nitrative cyclizations with high levels of chemo‐ and regioselectivity.