Recent Advances in Functional Group Transpositions in Arenes and Heteroarenes

Functional group transpositions in arenes and heteroarenes constitute a powerful tool in organic synthesis, enabling access to synthetically elusive compounds. Classical aromatic rearrangements, such as the Smiles, Claisen, and Bamberger reactions, allow positional reorganization but inevitably leave a residual substituent at the original ipso carbon, thereby precluding complete transfer. In contrast, a conceptually distinct yet underdeveloped class of transformations enables genuine positional transposition, in which a substituent undergoes net positional relocation within a pre‐existing or newly formed aromatic framework, thereby generating a different substitution pattern in the final aromatic product. This review delineates the conceptual boundaries among these processes and organizes previously scattered examples of functional group transposition, including transition‐metal‐enabled dissociation–recombination sequences, carbocation‐mediated processes, and multistep relay strategies, while also discussing closely related photochemical heterocycle isomerizations involving aromatic ring reconstruction as complementary strategies for positional editing. These advances highlight new opportunities to overcome intrinsic site‐selectivity limitations in aromatic synthesis.