Photo‐Mediated Aerobic Oxidation of Benzylic C–H Bonds and Alcohols by <i>N</i> ‐Center Radical

Abstract Photochemical strategies enable sustainable C─H bond activation under mild conditions via hydrogen atom transfer (HAT). Nitrogen‐centered radicals, particularly from N ‐fluorobenzenesulfonimide (NFSI), are effective HAT agents, but typically require complex catalytic systems. Here, we report a photo‐mediated protocol for aerobic oxidation of benzylic C( sp 3 )─H bonds using NFSI or Selectfluor without the need for metal‐ or photo‐catalyst. This method enables the direct synthesis of ketones and carboxylic acids from aryl alkanes under ambient conditions without directing groups. The same conditions also allow for alcohol oxidation and benzylic ether deprotection to phenol, demonstrating broad synthetic utility. This operationally simple strategy offers a sustainable alternative for late‐stage oxidation in organic synthesis.