Akin to the dihydroxylation, the oxyamination involves the cycloaddition of the alkene to an imido Os(VIII) intermediate of the type OsO3(NR). Such species are generated by treatment of osmium tetroxide with the sodium chloramines. Typical procedures combine chloramine-T, alkene, an osmium catalyst, and a chiral ligand.[2] Related procedures use benzyl carbamate (CbzNH2), sodium hydroxide, tert-butyl hypochlorite to give CbzNCl(Na).[3]
R2NH + t-BuOCl → R2NCl + t-BuOH
Further readingedit
Early papers in the development of this methodology.
Herranz, E.; Biller, S. A.; Sharpless, K. B. J. Am. Chem. Soc.1978, 100, 3596-3598. (doi:10.1021/ja00479a051)
Bäckvall, J. E.; Oshima, K.; Palermo, R. E.; Sharpless, K. B. J. Org. Chem.1979, 44, 1953. (doi:10.1021/jo01326a013)
Referencesedit
^Bodkin, J. A.; McLeod, M. D. J. Chem. Soc., Perkin Trans. 1, 2002, 2733–2746. (doi:10.1039/b111276g)
^Herranz, E.; Sharpless, K. B. (1983). "Osmium-Catalyzed Vicinal Oxyamination of Olefins by Chloramine-T: cis-2-(p-Toluenesulfonamido)cyclohexanol and 2-Methyl-3-(p-Toluenesulfonamido)-2-Pentanol". Org. Synth. 61: 85. doi:10.15227/orgsyn.061.0085.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^Herranz, Eugenio; Sharpless, K. Barry (1983). "Osmium-catalyzed Vicinal Oxyamination of Olefins by N-chloro-N-Argentocarbamates: Ethyl Threo-[1-(2-hydroxy-1,2-diphenylethyl)]carbamate". Org. Synth. 61: 93. doi:10.15227/orgsyn.061.0093.
January 01, 1970
sharpless, oxyamination, often, known, sharpless, aminohydroxylation, chemical, reaction, that, converts, alkene, vicinal, amino, alcohol, reaction, related, sharpless, dihydroxylation, which, converts, alkenes, vicinal, diols, vicinal, amino, alcohols, import. The Sharpless oxyamination often known as Sharpless aminohydroxylation is the chemical reaction that converts an alkene to a vicinal amino alcohol The reaction is related to the Sharpless dihydroxylation which converts alkenes to vicinal diols 1 Vicinal amino alcohols are important products in organic synthesis and recurring pharmacophores in drug discovery The Sharpless oxyaminationMechanism editAkin to the dihydroxylation the oxyamination involves the cycloaddition of the alkene to an imido Os VIII intermediate of the type OsO3 NR Such species are generated by treatment of osmium tetroxide with the sodium chloramines Typical procedures combine chloramine T alkene an osmium catalyst and a chiral ligand 2 Related procedures use benzyl carbamate CbzNH2 sodium hydroxide tert butyl hypochlorite to give CbzNCl Na 3 R2NH t BuOCl R2NCl t BuOHFurther reading editEarly 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 doi 10 1021 ja00841a071 Herranz E Biller S A Sharpless K B J Am Chem Soc 1978 100 3596 3598 doi 10 1021 ja00479a051 Backvall J E Oshima K Palermo R E Sharpless K B J Org Chem 1979 44 1953 doi 10 1021 jo01326a013 References edit Bodkin J A McLeod M D J Chem Soc Perkin Trans 1 2002 2733 2746 doi 10 1039 b111276g Herranz E Sharpless K B 1983 Osmium Catalyzed Vicinal Oxyamination of Olefins by Chloramine T cis 2 p Toluenesulfonamido cyclohexanol and 2 Methyl 3 p Toluenesulfonamido 2 Pentanol Org Synth 61 85 doi 10 15227 orgsyn 061 0085 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Herranz Eugenio Sharpless K Barry 1983 Osmium catalyzed Vicinal Oxyamination of Olefins by N chloro N Argentocarbamates Ethyl Threo 1 2 hydroxy 1 2 diphenylethyl carbamate Org Synth 61 93 doi 10 15227 orgsyn 061 0093 Retrieved from https en wikipedia org w index php title Sharpless oxyamination amp oldid 1118575108, wikipedia, wiki, book, books, library,
