Reductive Aminomethylative Cyanoalkylation of Alkenes with Sodium Iodide as a Terminal Reductant

The reductive dicarbofunctionalization of alkenes represents a powerful platform for the rapid construction of complex motifs from abundant materials by forging two chemical bonds in a single operation. Despite significant progress, the use of excessive reductants remains largely limited to environmentally unfriendly metal reductants or pyrophoric/expensive organic reductants, which may lead to serious environmental pollution, high costs, and low functional group tolerance. By leveraging NaI, rarely employed as a reductant in coupling reactions, we developed a novel reductive aminomethylcyanoalkylation of alkenes accelerated by iron electron-shuttle catalysis, allowing for the synthesis of sterically congested amino nitriles, valuable yet synthetically challenging motifs in organic synthesis. Mechanistic studies further confirmed that sodium iodide serves as the decisive terminal reductant.