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Synfacts 2006(11): 1175-1175  
DOI: 10.1055/s-2006-949454
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart · New York

Organocatalytic Asymmetric Kornblum-DeLaMare Rearrangement

Contributor(s): Benjamin List, Corinna Reisinger
S. T. Staben, X. Linghu, F. D. Toste*
University of California, Berkley, USA
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Publication History

Publication Date:
24 October 2006 (online)

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Significance

The first asymmetric version of the base-catalyzed Kornblum-DeLaMare rearrangement has been developed and applied to the desymmetrization of meso-endoperoxides resulting in the synthesis of γ-hydroxyenones. Six- to eight-membered, differently substituted products are accessible in good to excellent enantiomeric ratios. As chiral catalysts, the authors employed a cinchona alkaloid derivative. They proposed that the modified quinidine acts as a bifunctional Brønsted base/Brønsted acid catalyst promoting the enantiodetermining deprotonation via an E2-elimination mechanism. Furthermore, an example of a one-pot variant starting from the 1,3-diene is reported.