“…N -Hydroxybenzimidazoles, which are planar and stable heterocycles bearing an N -hydroxy moiety, have recently attracted interest in the field of biological and pharmaceutical sciences as anti-virulence or anti-cancer agents. 9 , 10 However, they have rarely been used in synthetic organic chemistry and, to the best of our knowledge, studies on the potential of NHBIs to generate the corresponding N -oxyl radicals have not yet been conducted. 11 In this context, we became interested in the potential of NHBIs as novel organoradical precursors based on the following features: (1) NHBIs can be readily prepared from 2-nitroaniline derivatives in a few steps (see the ESI † ); (2) substituents can be easily introduced at both the aromatic ring and the 2-position of the benzimidazole moiety; (3) NHBIs contain additional modification sites such as the nitrogen atom at the 3-position of the benzimidazole moiety and the counteranion of the resulting benzimidazolium species, which may potentially be exploited for further functionalization.…”