Building on these mechanistic studies and previous reports, we proposed two plausible catalytic cycles for the model arylative radical cross-coupling reactions without or with light irradiation (Figure ). It was postulated that the arylative radical cross-coupling of 2-vinylnaphthalene 1a and somewhat background reaction of 4-alkyl 1,3-enyne 8a should proceed through non-photoinduced catalytic cycle in the absence of visible light irradiation (Figure ). Initially, the ground state LCu I complex A (L = L10 or L25) coordinates with oxime carbonate 2a to facilitate otherwise difficult SET-reduction of 2a, generating an iminyl radical 2a-A together with carboxylic anion (BocO -) and the LCu II species C. The BocO -species undergoes rapid decarboxylation to form tert-butoxyl anion (tert-BuO -), which can serve as a Lewis base to activate phenylboronic acid 3a to promote its transmetalation with LCu II species C to form LCu II /Ph complex D. Meanwhile, the initially formed iminyl radical 2a-A undergoes ring-opening β-C-C bond cleavage to form cyanoalkyl radical 2a-B. Intermolecular radical addition of 2a-B to either 2-vinylnaphthalene 1a or 4-alkyl 1,3-enyne 8a generates the more stabilized benzylic radical 1a-A or allenyl radicals 8a-B. Finally, radical intermediates 1a-A and 8a-B undergo enantioselective cross-coupling with species D to deliver the corresponding products 4a and 9a, respectively, with regeneration of the catalyst LCu I A.