Background: Rearrangements as an important class of organic reactions could provide structural
isomers of the original molecules. They can transform precursors into favorable difficult-to-make products.
One of the important synthetic tools in modern organic chemistry is the Smiles rearrangement and its different
variants, which have diverse applications in organic chemistry.
Objective: The Smiles rearrangement is one of the intramolecular nucleophilic aromatic substitution reactions
wherein incorporate a heteroatom as a nucleophile and an activated electrophilic arene. Regarding the importance
of nucleophiles’ role in the development of different variants of the Smiles rearrangement herein, we
have surveyed several examples of Smiles rearrangement with the emphasis on their nucleophiles’ types. Accordingly,
three classes of Smiles rearrangement, employing carbanion, oxygen and nitrogen as different nucleophiles
have been investigated which are accompanied with their detailed mechanisms.
Conclusion: Categorization of Smiles rearrangements according to their nucleophiles’ species provides the
better understanding about these rearrangements that could enhance the synthesis of useful chemical compounds
such as medicinal compounds, functional materials and so on. Representation of different aspects of
Smiles rearrangement such as their mechanisms and synthetic utility helps researchers understand and take advantage
of Smiles rearrangement to make a greater attempt to further development in this important class of