Smiles rearrangement

In organic chemistry, the Smiles rearrangement is an organic reaction and a rearrangement reaction named after British chemist Samuel Smiles.

[1][2] It is an intramolecular, nucleophilic aromatic substitution of the type: where X in the arene compound can be a sulfone, a sulfide, an ether or any substituent capable of dislodging from the arene carrying a negative charge.

The terminal functional group in the chain end Y is able to act as a strong nucleophile for instance an alcohol, amine or thiol.

This reaction is exemplified by the conversion of an aryl sulfone into a sulfinic acid by action of n-butyllithium:[3] This particular reaction requires the interaction of the alkyllithium group ortho to the sulfone group akin a directed ortho metalation.

A radical version of Smiles rearrangement is reported by Stephenson in 2015.