The direct and enantioselective organocatalytic alpha-oxidation of aldehydes

J Am Chem Soc. 2003 Sep 10;125(36):10808-9. doi: 10.1021/ja037096s.

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.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Aldehydes / chemistry*
  • Amination
  • Amino Alcohols / chemical synthesis
  • Oxidation-Reduction
  • Proline / chemistry*
  • Stereoisomerism

Substances

  • Aldehydes
  • Amino Alcohols
  • Proline