Direct catalytic enantioselective alfa-oxidation of ketones: A stereoselective synthesis of alfa- and alfa,alfa‘-di-hydroxy ketones

ORGN 472

Armando Córdova, Henrik Sundén, and Anders Bøgevig. Department of Organic Chemistry, Stockholm University, The Arrhenius Laboratory, Stockholm, 106 91, Sweden
Herein, we disclose the unprecedented catalytic alfa-oxidation of unmodified ketones. The reactions proceeded with remarkably high selectivities affording alfa-oxyaminated adducts with >99% ee. The transformations were highly regioselective and unsymmetrical ketones were furnished as a single regioisomer with >99% ee. Furthermore, one-step asymmetric synthesis of protected alfa, alfa’-di-hydroxy ketones with >99% ee was also achieved for the first time. In addition, the proline-catalyzed reaction provides a new stereoselective and very mild entry to either enantiomer of anti- or syn- 1,2 diols. The reactions were readily performed on multi-gram scale furnishing a low-cost entry for valuable chiral compounds.
 

Total Synthesis, Asymmetric Reactions and Syntheses, Bioorganic
9:00 AM-11:00 AM, Wednesday, March 31, 2004 Anaheim Convention Center -- Hall C, Poster

Sci-Mix
8:00 PM-10:00 PM, Monday, March 29, 2004 Anaheim Convention Center -- Hall A, Sci-Mix

Division of Organic Chemistry

The 227th ACS National Meeting, Anaheim, CA, March 28-April 1, 2004