Sharpless oxyamination

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The Sharpless oxyamination (often known as Sharpless aminohydroxylation) is the chemical reaction that converts an alkene to a vicinal amino alcohol.[1][2][3] A comprehensive review of this reaction was authored by McLeod et al. in 2002.[4] Vicinal amino-alcohols are important products in organic synthesis and recurring pharmacophores in drug discovery.[5]

The Sharpless oxyamination
Structure of OsO3(N-t-Bu) (multiple bonds are not drawn explicitly), illustrating the type of osmium(VIII)-oxo-imide that adds alkenes en route to the amino alcohol.[6]

Mechanism[edit]

The reaction proceeds by the addition of the alkene imido derivative of osmium tetroxide. Such imido derivatives are usually generated in situ. Subsequent to the cycloaddition, the intermediate Os(VI) derivative is hydrolyzed to release the amino alcohol. The Os(VI) complex is then reoxidized with a chloramine derivative or similar electrophilic nitrene source.

References[edit]

  1. ^ Sharpless, K. B.; Patrick, D. W.; Truesdale, L. K.; Biller, S. A. J. Am. Chem. Soc. 1975, 97, 2305. (doi:10.1021/ja00841a071)
  2. ^ Herranz, E.; Biller, S. A.; Sharpless, K. B. J. Am. Chem. Soc. 1978, 100, 3596-3598. (doi:10.1021/ja00479a051)
  3. ^ Herranz, E.; Sharpless, K. B. Org. Synth., Coll. Vol. 7, p.375 (1990); Vol. 61, p.85 (1983). (Article)
  4. ^ Bodkin, J. A.; McLeod, M. D. J. Chem. Soc., Perkin Trans. 1, 2002, 2733–2746. (doi:10.1039/b111276g)
  5. ^ Bäckvall, J. E.; Oshima, K.; Palermo, R. E.; Sharpless, K. B. J. Org. Chem. 1979, 44, 1953. (doi:10.1021/jo01326a013)
  6. ^ Brian S. McGilligan, John Arnold, Geoffrey Wilkinson, Bilquis Hussain-Bates, Michael B. Hursthouse (1990). "Reactions of Dimesityldioxo-Osmium(VI) with Donor Ligands; Reactions of MO2(2,4,6-Me3C6H2)2, M = Os or Re, with Nitrogen Oxides. X-Ray Crystal Structures of [2,4,6-Me3C6H2N2]+[OsO2(ONO2)2(2,4,6-Me3C6H2)], OsO(NBut)(2,4,6-Me3C6H2)2, OsO3(NBut), and ReO3[N(2,4,6-Me3C6H2)2]". J. Chem. Soc., Dalton Trans.: 2465–2475. doi:10.1039/DT9900002465.CS1 maint: Uses authors parameter (link)