Photoinitiated Aerobic α-C–H Oxidation of Amides Enabled by a Cerium(IV)-Nitrate LMCT Pathway

Ceric ammonium nitrate (CAN), a classical oxidant, is underutilized in photochemistry. We report a light-driven direct α-oxidation of amides via substoichiometric CAN, leveraging its ligand-to-metal charge transfer (LMCT) to generate NO₃^•, avoiding precious metals/toxic oxidants. It activates N-α C(sp³)-H bonds; aerobic oxidation with O₂ yields imides mildly. This strategy overcomes amide inertness, enabling C-H functionalization without preactivated substrates/toxic reagents.