Modern Aspects of the Smiles Rearrangement

Abstract The Smiles rearrangement is an intramolecular S N Ar reaction, breaking a C−X single bond and forming a new C−X or C−C bond though ipso substitution. Its vast scope, in terms of nucleophile, leaving group, and ring‐size of the transition state, make it a powerful tool for arene functionalization, as it can be employed strategically to switch easily‐forged bonds with more difficult connections that would be challenging to realize in the intermolecular mode. The reaction has received significantly renewed attention in recent years, as advances in areas such as arene C−X bond formation and radical generation have been harnessed for new arene syntheses through Smiles chemistry. In addition, new reaction modes have been discovered, such as the Clayden rearrangement of lithiated ureas, creating innovative applications for Smiles rearrangements in asymmetric arylation. This Minireview will discuss advances in these areas in the recent literature, covering both two‐electron, polar Smiles rearrangements along with single‐electron radical transformations.