Surface-mediated reactions. 9. Selective oxidation of primary and secondary amines to hydroxylamines.
OXONE over silica gel or, in some cases, alumina has been found to oxidize the primary and secondary amines 3 selectively to the corresponding hydroxylamines 4, in either the presence or absence of a solvent. Treatment of Boc-protected L-lysine (6) under the latter conditions afforded hydroxylamine 7 in excellent yield. The trialkylamine 1a and pyridine (1b), in which selectivity is not an issue, were readily oxidized to the corresponding oxides 2 by OXONE over silica gel or alumina, as well as by (CH(3))(3)COOH over silica gel. Solvent-free oxidation assisted by microwave irradiation was more forcing, while still affording the hydroxylamines 4 selectively, and is the synthetic method of choice. The mechanistic aspects of these reactions are discussed.
Fields
J D
JD
Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA.
Kropp
P J
PJ
D000537:Aluminum Oxide; D006898:Hydroxylamines / Q000737:chemistry*; D007202:Indicators and Reagents; D010084:Oxidation-Reduction; D013464:Sulfuric Acids; D013499:Surface Properties
D006898:Hydroxylamines; D007202:Indicators and Reagents; D013464:Sulfuric Acids; C048813:potassium peroxymonosulfuric acid; D000537:Aluminum Oxide