Naturally occurring conjugated allenynes are of general interest to the scientific community for their potent and various biological activities. The 1,5-H transfer of alka-1,4-diyn-3-yl amines would be one of the most straightforward yet challenging approach to this class of compounds since it may, in principle, form two regioisomeric products involving two different C-C triple bonds. Herein, a catalytic recipe of copper halides with mixed oxidation states, i.e., CuCl/CuBr₂, has been identified to address the issues of the side reaction of conjugate addition and the selectivity of 1,5-H transfer of the key intermediate, alka-1,4-diyn-3-yl amines, in EATA (Enantioselective Allenation of Terminal Alkynes) reaction involving the conjugated 2-alkynals. This protocol could accommodate a wide range of functional groups providing a series of allenynes with very high enantioselectivity (up to >99% ee). In addition, the enantioenriched allenynes can be readily transformed into various building blocks and applied to the highly enantioselective total synthesis of linear allenic natural product scorodonin for the first time. Mechanistic studies and DFT calculations elucidated the high regioselectivity for observed 1,5-H transfer within the intermediate of 1,4-diyn-3-yl amines. The calculated energy difference between two of the most stable transition states of 3.4 kcal/mol accounts for a selectivity of over 99:1, which is in perfect agreement with the experimental results. Link