Photochemical Synthesis of DNA-Encoded 3 <i>H</i> -Azepines via Skeletal Editing of Nitroarenes

We report a skeletal editing strategy based on DNA-encoded nitroarenes for the direct conversion of benzene cores into valuable 3 H -azepine scaffolds. This transformation is efficiently promoted by visible light in the presence of P(O i -Pr) 3, which serves as a reductant to generate reactive nitrene intermediates from the nitro group. Demonstrating broad substrate scope with applicability to pharmaceutical molecules, this protocol offers an efficient and versatile route to DNA-encoded 3 H -azepine derivatives. It thus establishes a robust platform for skeletal diversification in DNA-encoded library synthesis.