Osmium Tetroxide
Osmium tetraoxide cis hydroxylation of unsaturated substrates
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Asymmetric Dihydroxylation of Alkenes·
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The OsO4 cis-hydroxylation of alkenes directly introduces vicinal hydroxy groups, and this may be the ultimate goal (as in the synthesis of Sativenediol below). However many other subsequent transformations of the diol lead to other functionalities. The most common is C-C bond cleavage of the diol with NaIO4 or Pb(OAc)4 to give aldehydes or ketones (Anatoxin), but many other transformations can be performed, such as Peterson olefination (Conduritol), reduction to mono alcohol (Adaline), oxidation to α-hydroxy ketones or α-diketones (Cephalotaxine).
For most applications OsO4 is too expensive and toxic to use stoichiometrically, so it is usually used catalytically together with a stoichiometric oxidant, most commonly an amine oxide (N-methylmorpholine N-oxide (NMO) or trimethylamine oxide). If the goal is to cleave the double bond (and this is the most common use of OsO4), then sodium or potassium periodate is used, it functions as both reoxidant and diol cleavage agent.
Sativenediol: Sigrist, R.; Rey, M.; Dreiding, A. Helv. Chem. Acta 1988, 71, 788. DOI
Anatoxin A: Brenneman, G. B.; Martin, S. F. Org. Lett. 2004, 6, 1329
In the example below a bis-hydroxylation followed by reductive removal of one of the OH groups is equivalent to a regio- and stereo-selective hydration of the double bond. Adaline: Itoh, T.; Yamazaki, N.; Kibayashi, C. Org. Lett. 2002, 4, 2469. DOI
Conduritol B, F: Heo, J. N.; Holson, E. B.; Roush, W. R. Org. Lett. 2003, 5, 1697-1700
Cephalotaxine: Isono, N,; Mori, M. J. Org. Chem. 1995, 60, 115-119
Warburganal: Wender. P. A.; Eck, S. L Tetrahedron Lett. 1982, 23, 1871. DOI
