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    The Direct and Enantioselective Organocatalytic α-Oxidation of Aldehydes
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    Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125
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    Cite this: J. Am. Chem. Soc. 2003, 125, 36, 10808–10809
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    https://doi.org/10.1021/ja037096s
    Published August 19, 2003
    Copyright © 2003 American Chemical Society

    Abstract

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    The first direct enantioselective catalytic α-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 α-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.

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    Published August 19, 2003
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