Smiles rearrangement

The Smiles rearrangement is an organic chemical reaction and is one of the rearrangement reactions.

Is an intramolecular nucleophilic aromatic substitution. The group X can act here a sulfone, sulfide, ether, or other electron-withdrawing substituents. The group Y has to be a strong nucleophile such as phenol oxygen atom, the amine nitrogen atom, or sulfur. As with other nucleophilic substitution of aromatic compounds must be activated by other electron-withdrawing groups in the ortho or para position to the X group.

A variant of the Smiles rearrangement is known as the Truce - Smiles rearrangement. Here, the nucleophile Y is so severe that the aromatic compound must not contain any other activating groups. As nucleophiles serve organolithium compounds here.

The reaction uses the ortho- sulfone group from the anion by an ortho- metalation to produce as a nucleophile.

A similar rearrangement reaction is known as the Chapman rearrangement.