A highly enantioselective copper-catalyzed propargylic amination starting from benzylicallylic amines has been developed with a new chiral N,N,P ligand. A series of N-tethered 1,6-enynes were synthesized in good to excellent yields with excellent enantioselectivities. Utilization of transition metal-catalyzed cycloisomerization of 1,6-enynes provides several enantioselectively enriched chiral five-membered