Portal de Periódicos da CAPES

Surface-Mediated Reactions. 9. Selective Oxidation of Primary and Secondary Amines to Hydroxylamines 1

2000; American Chemical Society; Volume: 65; Issue: 19 Linguagem: Inglês

10.1021/jo0002083

1520-6904

John D. Fields, Paul J. Kropp,

Inorganic and Organometallic Chemistry

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 (CH3)3COOH 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.