- Smiles rearrangement
The Smiles rearrangement is an
organic reaction and arearrangement reaction . [A. A. Levy, H. C. Rains and S. Smiles, J. Chem. Soc. 1931, 3264.] It is anintramolecular nucleophilic aromatic substitution of the type:where X in the
arene compound can be asulfone , asulfide , anether or anysubstituent 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 strongnucleophile for instance analcohol ,amine orthiol .As in other
nucleophilic aromatic substitution s the arene requires activation by anelectron-withdrawing group preferably in thearomatic ortho position .In one modification called the Truce-Smiles rearrangement the incoming nucleophile is sufficiently strong that the arene does not require this additional activation, for example when the nucleophile is an
organolithium . This reaction is exemplified by the conversion of anaryl sulfone into ansulfinic acid by action of "n"-butyllithium: ["Rearrangements of Aryl Sulfones. I. The Metalation and Rearrangement of Mesityl Phenyl Sulfone" William E. Truce, William J. Ray, Oscar L. Norman, and Daniel B. EickemeyerJ. Am. Chem. Soc. ; 1958; 80(14) pp 3625 - 3629; DOI|10.1021/ja01547a038]This particular reaction requires the interaction of the alkyllithium group ortho to the sulfone group akin a
directed ortho metalation .A conceptually related reaction is the
Chapman rearrangement .External links
* Appearance in
Organic syntheses : Org. Synth. 2007, 84, 325-333 [http://www.orgsynth.org/orgsyn/pdfs/V84P0325.pdf Article]References
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