title: The direct and enantioselective organocatalytic alpha-oxidation of aldehydes.
abstract: The first direct enantioselective catalytic alpha-oxidation of carbonyls has been accomplished. The use of enamine catalysis has provided a new organocatalytic strategy for the enantioselective oxyamination of aldehydes, to generate alpha-oxyaldehydes, important chiral synthons for natural product and medicinal agent synthesis. The use of l-proline as the asymmetric catalyst has been found to mediate the oxidation of a large variety of aldehyde substrates with nitrosobenzene serving as the electrophilic oxidant. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. While catalyst quantities of 2 mol % were generally employed in this study, successful oxidations conducted using catalyst loadings as low as 0.5 mol % are described.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Sean P
authors.initials: SP
authors.lastname: Brown
authors.forename: Michael P
authors.initials: MP
authors.lastname: Brochu
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Sinz
authors.forename: David W C
authors.initials: DW
authors.lastname: MacMillan
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000586:Amination; D000605:Amino Alcohols / Q000138:chemical synthesis; D010084:Oxidation-Reduction; D011392:Proline / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D000605:Amino Alcohols; D011392:Proline