The preliminary mechanistic investigations paralleled prior reports regarding aroyl radical generation, Stern-Volmer quenching, and radical-chain propagation. Notably, the absence of -alkoxylated product 15.10 in reactions with -hydroxy adducts negated the involvement of an N-acyliminium ion intermediate (Figure ). Collisioninduced fragmentation indicated the formation of copper complex (15.12). Based on these findings, an inner-sphere interaction between the Cu catalyst and 15.17 is proposed (Figure ). Subsequent intramolecular condensation, ligand exchange, Cu-migration, and reductive elimination provided the -hydroxylated or -alkoxylated products; however, in the absence of alcohol or water, 15.19 undergoes protonation and tautomerization to yield the hydrogenated product. The 2-aminophenol motif holds significant pharmaceutical relevance, serving as a key structural motif in numerous marketed drugs for diarrhoea, lung carcinoma, and plaque psoriasis. Despite its importance, methodologies for synthesizing these scaffolds remain relatively underrepresented in literature. Recently, Ngai et. al. designed a radical coupling followed by a migration strategy involving excited nitro(hetero)arenes and acyl radicals to access these structures (Figure ). They employed a Cu(I)-BINAP catalytic system under visible light to access a broad array of acyl radicals from acyl chlorides and couple them with the triplet state (T1) of various functionalized nitro(hetero)arenes (Figure ).