Catalyst‐Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides

A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials. By‐pass: Nitro compounds are directly coupled with (functionalized) organohalides to yield monoalkylated amines. As nitroso intermediates are by‐passed, not only aromatic but also aliphatic nitro compounds are efficiently transformed. The nitrenoid's innate reactivity makes a catalyst unnecessary. Therefore, the reaction is orthogonal to traditional reductive couplings and aryl halide substituents are well tolerated in both starting materials.