To further validate the feasibility of photoredox pathway and to shed light on the observed regioand chemoselectivity, DFT studies were conducted (Fig. ). Firstly, the excited-state Ir(III) photocatalyst, generated upon irradiation, undergo single electron transfer (SET) with N-amidocollidinium tetrafluoroborate 2d leading to the formation of oxidized species Ir(IV) and an amidyl radical Int-1 (Supplementary Fig. ). The subsequent addition of amidyl radical across the inter-bridgehead C1-C3