RESUMO
A general and modular protocol is reported for olefin difunctionalization through mechanochemistry, facilitated by cooperative radical ligand transfer (RLT) and electron catalysis. Utilizing mechanochemical force and catalytic amounts of 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), ferric nitrate can leverage nitryl radicals, transfer nitrooxy-functional group via RLT, and mediate an electron catalysis cycle under room temperature. A diverse range of activated and unactivated alkenes exhibited chemo- and regioselective 1,2-nitronitrooxylation under solvent-free or solvent-less conditions, showcasing excellent functional group tolerance. Mechanistic studies indicated a significant impact of mechanochemistry and highlighted the radical nature of this nitrative difunctionalization process.