An unprecedented stereospecific allylation reaction of nitroacetates with enantioenriched primary allylic amines has been developed. A range of nitroacetates smoothly underwent allylation with enantioenriched primary allylic amines in the presence of a palladium catalyst and boric acid followed by one‐pot decarboxylation to afford structurally diverse homoallylic nitro compounds in good to excellent yields with excellent retention of configuration. On the other hand, the allylation followed by denitronation provided a facile synthetic route to optically active β‐chiral γ,δ‐unsaturated esters.
