Abstract: | A redox‐neutral, light‐mediated functionalization of unactivated C(sp3)?H bonds via iminyl radicals is presented here. A 1,5‐H transfer followed by the functionalization of a C(sp2)?H bond takes place in aqueous media producing a variety of elaborated fused ketones. Mechanistic investigations have revealed 1,5‐H transfer as the reversible, rate‐determining step in this transformation. Divergent scaffolds are also accessible via C(sp3)?N bond formation upon a careful choice of the reaction additives. |