Smiles Rearrangement
Smiles rearrangement is an intramolecular nucleophilic substitution which involves the attacking on an aromatic system possessing an activating electron-withdrawing group at ortho- or para-position to the reaction centre connected to a heteroatom. Smiles rearrangement is further involves the migration of an aromatic ring from the heteroatom binding to the reaction center to a more nucleophilic heteroatom.
X may be S, SO, SO2, O or COO and YH may be OH, NH2, NHR or SH. The reaction has also been carried out with YH = CH3 (PhLi was used as base) in this particular case the rearrangement is known as Truce-Smiles rearrangement.
![](https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgnoy3dq6Q4Rvx8CAY-52w1YqRT9RUJvq7-u6Aej3C9V-rNlvQ6nOQE-5ffZuewbg1Evs7Pa2o5E4oLERe2MaOSN6cea-HRnKMCsuAARAYnYkE4UibdMmC_5zomaHLQ9CPVyWqRo_Tf_Y25qtRiRM9baTGqQu4nIJRIqy-qNW0fCf3iNbn3AeTA9-7ky0vn/s1600/Smiles%20Rearrangement.gif)
Mechanism of Smiles Rearrangement
The presence of EWG para to the YH group in the substrate retards the rate of the smiles rearrangement because such groups reduce the nucleophilicity of Y−.
![Smiles Rearrangement Limitation](https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEhNh9W9YzKzg29lzYRHNGwfL0KJDlkIDc-aUh9lrFpX5ALuAiY3VBx0Si0w7ek2W6kCxK7gD61F4TfrQp-g62gZGTiBKoeBUPhIGMG_T1Zxnf2e8ZicCcRtLoaYtWKX00G4cpYX2JSlJPUSwm6mrCwJoKf9eCqp5wHcC1UOePL7yuoYd6WlpAmT1nSolJQf/s1600/Smiles%20Rearrangement%20limitation.gif)
Z and Z' are activating groups for nucleophilic aromatic substitution reaction. Z and/or Z' should be an EWG such as -NO2, -CN or CF3 to stabilize the cyclohexadienylide anion formed.