Previous studies have established the intermediacy of propargylic radicals during the radical addition of 1,3-enynes. We envisioned that introduction of an aryl group at the propargylic position can also access the allenyl radicals through resonate; the subsequent asymmetric arylative cross-coupling with boronic acids would offer a novel approach toward challenging and previously inaccessible chiral tetrasubstituted allenes. Based on this design plan, and using the model three-component cross-coupling of 2phenyl-1,3-enyne 8a with oxime carbonate 2a and phenylboronic acid 3a, we performed a systematic investigation of the concentration, solvent, and ligand (see Supporting Information, section 3.3). The optimization studies indicate that a combination of 5 mol% of Cu(CH3CN)4PF6 and 6 mol% of chiral bisoxazoline ligand L25 as the catalyst, in a mixed solvent system of toluene/CH3CN/CPME with irradiation of visible light using a 20 W blue LEDs at 0 °C is optimal for this process (Table ). Under these conditions, the desired product 9a was isolated in 71% isolated yield and with excellent enantioselectivity (93% ee).