The scope of the aryl component (Figure ) was also assessed under the scheme of (Cu/Cu)-catalyst system with several α,β-unsaturated amides and esters, which showcased that a range of diaryliodonium salts could be successfully employed (3ai-3at). Substituents on the aryl group could be incorporated at the ortho, meta and para positions with halogens, alkyl groups and electron-donating groups (3ak-3aq). Aryl groups bearing electron-withdrawing substituents also worked satisfactorily (3aj, 3at). Transfer of thienyl and pyridyl units from the corresponding symmetrical diaryliodonium salts was also proved viable, albeit in a slightly diminished yield (3ar, 3as). Aryl group transfer from unsymmetrical iodonium salts was not evaluated since radical-mediated aryl transfer displays modest selectivity amidst differentially substituted arenes, which has been proved in the previous aryl-chlorination of vinyl boronic esters. The dual catalytic and modular alkene aryl-chlorination enables direct access to β-aryl alkyl chlorides, the likes of which have found widespread application in transformations such as: transition metal catalyzed enantio-convergent C-C 24 and C-N 25 bond formation processes; synthesis of hetereocycles via N-heterocyclic carbene catalysis ; reductive coupling reactions 27 ; and classical substitution reactions of the C-Cl bond 28 . Finally, attention was focused on gaining an understanding the mechanism of the dual catalytic process. Initial investigations focused on classical experimental evidence for the presence of aryl radical int-I and homobenzylic radical int-II through a chloro-arylation reaction using acrylonitrile and 2,2,6,6-tetramethylpiperidin-1yl)oxyl (TEMPO) as a radical scavenger. As expected, we observed the TEMPO-adducts of both the aryl radical and homobenzyl radical, thereby confirming the elementary steps of the pathway (See Supporting Information V.1)