The Sharpless oxyamination (often known as Sharpless aminohydroxylation) is the
chemical reaction
A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
that converts an alkene to a vicinal
amino alcohol
In organic chemistry, alkanolamines are organic compounds that contain both hydroxyl () and amino (, , and ) functional groups on an alkane backbone. The term alkanolamine is a broad class term that is sometimes used as a subclassification.
Meth ...
. The reaction is related to the
Sharpless dihydroxylation
Sharpless asymmetric dihydroxylation (also called the Sharpless bishydroxylation) is the chemical reaction of an alkene with osmium tetroxide in the presence of a chiral quinine ligand to form a vicinal diol. The reaction has been applied to alk ...
, which converts alkenes to vicinal diols. Vicinal amino-alcohols are important products in
organic synthesis and recurring
pharmacophore
300px, An example of a pharmacophore model.
A pharmacophore is an abstract description of molecular features that are necessary for molecular recognition of a ligand by a biological macromolecule. IUPAC defines a pharmacophore to be "an ensemble o ...
s in
drug discovery.
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,
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.
The ''Journal of the American Chemical Society'' is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the ''Journal of Analytic ...
'' 1975, ''97'', 2305. ()
*Herranz, E.; Biller, S. A.; Sharpless, K. B. ''
J. Am. Chem. Soc.
The ''Journal of the American Chemical Society'' is a weekly peer-reviewed scientific journal that was established in 1879 by the American Chemical Society. The journal has absorbed two other publications in its history, the ''Journal of Analytic ...
'' 1978, ''100'', 3596-3598. ()
*Bäckvall, J. E.; Oshima, K.; Palermo, R. E.; Sharpless, K. B. ''
J. Org. Chem.
''The Journal of Organic Chemistry'', colloquially known as ''JOC'', is a peer-reviewed scientific journal for original contributions of fundamental research in all branches of theory and practice in organic and bioorganic chemistry. It is publ ...
'' 1979, ''44'', 1953. ()
References
{{Reflist
Organic redox reactions
Name reactions