Smiles Rearrangement; Truce-Smiles Rearrangement

A. A. Levi et al., J. Chem. Soc. 1931, 3264; W. J. Evans, S. Smiles, ibid. 1935, 181; 1936, 329.

Intramolecular nucleophilic aromatic substitution in alkaline solution resulting in the migration of an aromatic system from one heteroatom to another. The two-carbon unit joining X and Y is usually part of an aromatic ring but may also be aliphatic:

The conversion of o-methyldiaryl sulfones to o-benzylbenzenesulfinic acids is referred to as the Truce-Smiles rearrangement: W. E. Truce et al., J. Am. Chem. Soc. 80, 3625 (1958); G. P. Crowther, C. R. Hauser, J. Org. Chem. 33, 2228 (1968).

Early reviews: J. F. Bunnett, R. E. Zahler, Chem. Rev. 49, 362 (1951); H. J. Shine, Aromatic Rearrangements (Elsevier, New York, 1967) pp 307-316; W. E. Truce et al., Org. React. 18, 99-215 (1970). Conversion of phenols to anilines: I. G. C. Coutts, M. R. Southcott, J. Chem. Soc. Perkin Trans. I 1990, 767. Kinetic study: K. Bowden, P. R. Williams, J. Chem. Soc. Perkins Trans. II 1991, 215. Methods development for aliphatic substrates: M. Sako et al., Chem. Pharm. Bull. 42, 806 (1994). Application to the synthesis of phenothiazines: S. K. Mukherjee et al., Pharmazie 49, 453 (1994); J. Mukesh et al., ibid. 689.