Direct Reductive N‐Functionalization of Aliphatic Nitro Compounds

The first general protocol for the direct reductive N‐functionalization of aliphatic nitro compounds is presented. The nitro group is partially reduced to a nitrenoid, with a mild and readily available combination of B2pin2 and zinc organyls. Thereby, the formation of an unstable nitroso intermediate is avoided, which has so far severely limited reductive transformations of aliphatic nitro compounds. The reaction is concluded by an electrophilic amination of zinc organyls. No N=O! The first general protocol for a direct reductive N‐functionalization of aliphatic nitro compounds is presented. This type of transformation was so far limited to nitro compounds devoid of α‐protons, due to the fast nitroso‐oxime tautomerization. N‐functionalization is enabled by an alternative reaction path via a more stable nitrenoid intermediate.