Aiming at the development of new photolabeling agents, the synthesis and photoreactivity of all monofluorinated derivatives of 2-azido-1-methylbenzimidazole are described. In the case of 4-, 5-, or 7-fluorination, irradiation in the presence of carboxylic acids (300 nm, Rayonet) afforded the monofluorinated 2-amino-6-acyloxybenzimidazoles in a regioselective manner, presumably after conversion of the initially formed nitrene to the N-cyanodiazaxylylene. Incorporation of chloride was also possible, and yields were comparable to those observed for the non-fluorinated parent compound. When blocking the reactive 6-position by a fluoro substituent, the title reaction was not possible. The analysis of the 19F NMR chemical shifts of the 5- and 7-monofluorinated products allowed the distinction between carboxylates and other nucleophiles.

The photoreactivity of a series of hitherto unknown, multiply fluorinated 2-azidobenzimidazole derivatives was investigated. The synthesis of the starting material includes regioselective pdefluorination 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 arylesters by oxygenation of the 6position in good to excellent yields and perfect regioselectivity. We did not observe any displacement of fluoride. If the 6position itself was fluorinated, alternative positions of the benzene portion were attacked. Mechanistically, the reaction proceeds through ring opening of the singlet nitrene to the cyanodiimine or via the iminobenzimidazolium ion. The availability of a set of fluorinated photo-adducts prompted the quantum chemical calculation of their 19 F NMR chemical shifts. Even with the most suitable method investigated (ωB97XD/ TApr-cc-pVDZ), deviations of up to 5 ppm from the experimental values were observed, underlining the importance of experimental measurements.