Transition Metal‐Free Aromatic C−H, C−N, C−S and C−O Borylation

Abstract Aromatic organoboron compounds are highly valuable building blocks in organic chemistry. They were mainly synthesized through aromatic C−H and C−Het borylation, in which transition metal‐catalysis dominate. In the past decade, with increasing attention to sustainable chemistry, numerous transition metal‐free C−H and C−Het borylation transformations have been developed and emerged as efficient methods towards the synthesis of aromatic organoboron compounds. This account mainly focuses on recent advances in transition metal‐free aromatic C−H, C−N, C−S, and C−O borylation transformations and provides insights to where further developments are required.