As anticipated from the optimization studies the use of the Cu(I)-BPA salt as a pre-catalyst alongside [Cu(I)(dpp)2](PF6) as photocatalyst proved to be excellent reaction conditions for the successful transformation of electron-deficient alkenes (3u-3ah, Figure ). In several cases, β-arylethyl alkyl chlorides containing three orthogonal functionalities on the same carbon atom could be formed from this modular process, which would be challenging to obtain through established methods but useful for programmable downstream bond forming processes. Methyl arylate and acrolein, substrates that are often subject to radical-mediated polymerization, effectively produced β-aryl, a-chloro ester 3v (72%) and aldehyde 3y (76%); hydroxyl and halide motifs were also tolerated well, leading to 3aa and 3ab in 51% and 76%, respectively. α,β-Unsaturated alkenes bearing a remote pyridyl group also gave rise to the desired aryl-chlorination adduct 3ae in 60% yield, advocating the compatibility of the Cu-Cu catalyst system with Lewis basic functionality. Other alkenes displaying anilides and phthalimides were accommodated by the reaction and led to formation of 3af and 3ag in synthetically useful yields. In particular, 3ag represents a highly functionalized β-amino acid scaffold. The successful aryl-chlorination of isoalantalactone (2ah), a natural product bearing two distinct alkenes, demonstrated that the (Cu/Cu)-catalyst system is chemoselective for the electron-deficient alkene.