ABSTRACT A novel, metal‐free, boron‐mediated chemoselective aromatic C–H hydroxylation is reported. This transformation was discovered serendipitously during our investigation of water complexation with the boron/nitrogen (B/N) multiple resonance (MR) compound DtBuCzB. In the presence of hydrogen peroxide, the reaction proceeds via an initial oxidative boration followed by hydroxylation, enabling the installation of three hydroxyl groups in a single step with high ortho selectivity. The resulting polyhydroxylated framework provides versatile synthetic handles for further functionalization, underscoring the broad utility of this methodology. Overall, this strategy offers a convenient and practical route to densely functionalize aromatic compounds. This finding also raises a critical caveat regarding the long‐term storage of B/N‐MR materials, as trace oxidants present in the environment may induce unintended oxidative transformation.
Shi et al. (2026) studied this question.