Simple Chiral Diaminobinaphthyl Dilithium Salts for Intramolecular Catalytic Asymmetric Hydroamination of Amino‐1,3‐dienes

Simple and easily accessible chiral lithium amide salts are reported as efficient (pre)catalysts for the diastereo‐ [up to ( E : Z )=92:8] and enantioselective [up to 72% ee ( E )] hydroamination/cyclisation of conjugated primary aminodienes. These chiral lithium salts are straightforwardly prepared by in situ combination of an N ‐substituted ( R )‐(+)‐1,1′‐binaphthyl‐2,2′‐diamine ligand and a commercial methyllithium solution. Information on the solid‐state structure of these salts was obtained by X‐ray analysis of a single crystal.