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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.

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