A truce on the Smiles rearrangement: revisiting an old reaction--the Truce-Smiles rearrangement.

The Smiles rearrangement is the intramolecular nucleophilic aromatic substitution reaction incorporating a heteroatom as the nucleophilic component and an activated electrophilic arene. One particular variation--the Truce-Smiles rearrangement--utilises a carbon-based nucleophile and an electrophilic arene which does not require additional activation. Such a variation generates a new carbon-carbon bond and the synthetic utility of this relatively under-utilised rearrangement is discussed in this tutorial review.