The Sharpless oxyamination (often known as Sharpless aminohydroxylation) is the
chemical reaction
A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...
that converts an
alkene
In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins.
The Internationa ...
to a vicinal
amino alcohol. The reaction is related to the
Sharpless dihydroxylation, which converts alkenes to vicinal diols. Vicinal amino-alcohols are important products in
organic synthesis
Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...
and recurring
pharmacophores in
drug discovery
In the fields of medicine, biotechnology, and pharmacology, drug discovery is the process by which new candidate medications are discovered.
Historically, drugs were discovered by identifying the active ingredient from traditional remedies or ...
.
Mechanism
Akin to the dihydroxylation, the oxyamination involves the
cycloaddition of the alkene to an imido Os(VIII) intermediate of the type OsO
3(NR). Such species are generated by treatment of
osmium tetroxide
Osmium tetroxide (also osmium(VIII) oxide) is the chemical compound with the formula OsO4. The compound is noteworthy for its many uses, despite its toxicity and the rarity of osmium. It also has a number of unusual properties, one being that the ...
with the sodium chloramines. Typical procedures combine
chloramine-T, alkene, an osmium catalyst, and a chiral ligand. Related procedures use
benzyl carbamate (CbzNH
2),
sodium hydroxide
Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions .
Sodium hydroxide is a highly corrosive base (chemistry), ...
,
tert-butyl hypochlorite to give CbzNCl(Na).
:R
2NH + t-BuOCl → R
2NCl + t-BuOH
Further reading
Early papers in the development of this methodology.
*
Sharpless, K. B.; Patrick, D. W.; Truesdale, L. K.; Biller, S. A. ''
J. Am. Chem. Soc.'' 1975, ''97'', 2305. ()
*Herranz, E.; Biller, S. A.; Sharpless, K. B. ''
J. Am. Chem. Soc.'' 1978, ''100'', 3596-3598. ()
*Bäckvall, J. E.; Oshima, K.; Palermo, R. E.; Sharpless, K. B. ''
J. Org. Chem.'' 1979, ''44'', 1953. ()
References
{{Reflist
Organic redox reactions
Name reactions