Sulfoxide-Sulfenate Rearrangements
Stereochemistry of [2,3] Sigmatropic Rearrangements,
R. W. Hoffmann, Angew. Chem. Int. Ed. 1979, 18, 563.
[2,3] Sigmatropic Rearrangements of Organoselenium Compounds,
H. J. Reich in Organoselenium Chemistry, D. Liotta, Ed., Wiley, 1987.
Selenoxide Elimination and [2,3]-Sigmatropic Rearrangement,
Nishibayashi, Y.; Uemura, S. Top. Curr. Chem. 2000, 208, 201-35.
The sulfoxide-sulfenate equilibration was discovered by Mislow and coworkers during studies of the racemization barriers of sulfoxides. Allyl sulfoxides were found to racemize dramatically more rapidly than analogous alkyl sulfoxides. These workers also found that sulfenate esters, prepared by reaction of allyl alcohols with sulfenyl chlorides, rapidly rearranged to sulfoxides with a high equilibrium constant.
Racemization of sulfoxides: Mislow J. Am. Chem. Soc. 1966, 88, 3138, 3139.
When allyl sulfoxides are treated with thiophilic reagents like 1° or 2* amines, trivalent P compounds, or sulfur nucleophiles sulfoxides can be entirely converted to allyl alcohols by cleavage of the transient sulfenate ester. The reversible equilibration followed by cleavage provides an effective method for the inversion (or, rather equilibration) of allyl alcohol stereochemistry.
Isoamijiol: Majetich, G.; Song, J. S.; Ringold, C.; Nemeth, G. A. Tetrahedron Lett. 1990, 31, 2239
Preparation of allyl sulfoxides by cycloaddition: synthesis of Hasubanan alkaloid. Evans, D. A.; Bryan, C. A.; Sims, C. L. J. Am. Chem. Soc. 1972, 94, 2891
Conversion of Allyl Alcohols to 1,3-Dienes
Sequential [2,3]Sigmatropic/syn-Elimination of Allyl Sulfenate: Reich, Reich, Wollowitz, J. Am. Chem. Soc. 1982, 104, 7051.
Selenoetherification - Milbemycin/Avermectin Synthesis
M. T. Crimmins, W. G. Hollis, J. G. Lever, Tetrahedron Lett., 1987, 28, 3647.
Selenoxide Elimination; [2,3]Sigmatropic Rearrangement - Allylic functionalization.
Magnus, P.; Lewis, R.; Bennett, F. J. Am. Chem. Soc., 1992, 114, 2561.
Chorismic Acid: Sigmatropic Rearrangement of Sulfoxides.
Posner, JOC, 1987, 52, 4836.
5-Desoxyleucotriene D. Remote Oxidation Using Sigmatropic Rearrangements.
In the application below, an allylic sulfoxide anion is used to for a C-C bond, and the sulfoxide then migrates over 4 carbons to form a new sulfoxide. Corey, E. J.; Hoover, D. J. Tetrahedron Lett., 1982, 23, 3463.
Amines by Sigmatropic Rearrangement of Sulfimides and Selenimides.
The nirogen analogs of sulfoxide [2,3]sigmatropic rearrangements are also known: Hopkins, TL, 1984, 25, 15.
