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The photoreactivity of a series of hitherto unknown, multiply fluorinated 2‐azidobenzimidazole derivatives was investigated. The synthesis of the starting material includes regioselective p‐defluorination of nitrobenzene derivatives employing Ogoshi's conditions. If the 6‐position was unsubstituted, irradiation in the presence of N‐protected amino acids at 300 nm (Rayonet) led to the formation of...