Acids. Alkynes that contain propargylic stereogenic centers are an important class of structural scaffolds (Fig. ). In recent years, significant advances have been made towards the catalytic asymmetric construction of chiral benzylic alkyne derivatives, using twoor three-component cross-coupling reactions of benzylic radicals with nucleophilic alkynes. Notably, the groups of Xiao, Lu, and Lan, disclosed the first example of asymmetric cyanation of propargyl ester-derived propargylic radical with TMSCN as cyanide source by a synergetic photoredox and copper catalysis. Recently, Wang et al. reported an elegant two-component nickel-catalyzed asymmetric reductive cross-coupling of propargylic chlorides and aryl iodides, which provides practical access to chiral benzylic alkynes. Encouraged by the success of our asymmetric three-component arylative cross-coupling of styrene derivatives, we envisioned that this strategy could be extended to 1,3-enynes. The successful outcome of this process would, for the first time, provide a modular and alternative method for construction of cyano-alkylated chiral benzylic alkynes under redox-neutral conditions.