A catalytic enantioselective method for the formation of alkyne-substituted all-carbon quaternary stereogenic centers is reported. Additions of alkynylaluminums to alkyl-, aryl-, carboxylic ester-, or silyl-substituted allylic phosphates are promoted by 1.0-5.0 mol % loadings of NHC-Cu complexes derived from air-stable and commercially available CuCl2 center dot 2H(2)O. The requisite Al-based reagents are prepared through treatment of the corresponding aryl-, heteroaryl-, alkyl-, or alkenyl-substituted terminal alkynes with diisobutylaluminum hydride in the presence of 5.0 mol % Et3N at ambient temperature. The desired 1,4-enynes are obtained in up to 98% yield and > 99:1 enantiomeric ratio. Selected Au-catalyzed cyclizations involving the alkyne unit of the enantiomerically enriched products are presented as a demonstration of the method's utility in chemical synthesis.