Direct and Enantioselective Organocatalytic α-Chlorination of Aldehydes

Michael P. Brochu, Sean P. Brown, and David W. C. MacMillan*
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125
J. Am. Chem. Soc., 2004, 126 (13), pp 4108–4109
DOI: 10.1021/ja049562z
Publication Date (Web): March 11, 2004
Copyright © 2004 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, dmacmill@caltech.edu

Abstract

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The first direct enantioselective catalytic α-chlorination of aldehydes has been accomplished. The use of enamine catalysis has provided a new organocatalytic strategy for the enantioselective chlorination of aldehydes to generate α-chloro aldehydes, an important chiral synthon for chemical and medicinal agent synthesis. The use of imidazolidinone 3 as the asymmetric catalyst has been found to mediate the halogenation of a large variety of aldehyde substrates with the perchlorinated quinone 1 serving as the electrophilic chlorinating reagent. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. The capacity of catalyst 3 to override the inherent bias of resident stereogenicity in the chlorination of enantiopure β-chiral aldehydes is also described. Catalyst quantities of 5 mol % were generally employed in this study.

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History

  • Published In Issue April 07, 2004
  • Received January 25, 2004

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