Synthesis of chiral, non-racemic cyclopentenones from allylic hydroxy phosphonates

ORGN 273

Christopher D. Spilling1, Bingli Yan, biy4@pitt.edu2, and Saibal Bandyopadhyay, saibalban@yahoo.com1. (1) Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Blvd., St. Louis, MO 63121, (2) Department of Chemistry, University of Pittsburgh, 815 Chevron Science Center, 219 Parkman Ave., Pittsburgh, PA 15260
Cyclopentane-containing natural products are widely distributed throughout nature and methods for their synthesis are in demand. A new approach to chiral, non-racemic cylcopentenones will be described. Either a Pd (0)-catalyzed Carroll rearrangement, the addition of acetoacetate and decarboxylation, or a Claisen rearrangement on the appropriate allylic hydroxy phosphonate derivatives gave the keto vinyl phosphonates. Regioselective Wacker oxidation gave the diketo phosphonate, which underwent a intramolecular Wadsworth-Emmons reaction or an aldol condensation to the cyclopentenone and the phosphono cyclopentenone, respectively. Progress in the application of this chemistry to the synthesis of myomontanone will also be presented.

 

Asymmetric Reactions and Syntheses
8:00 AM-12:00 PM, Monday, 14 March 2005 Convention Center -- Room 11A, Oral

Division of Organic Chemistry

The 229th ACS National Meeting, in San Diego, CA, March 13-17, 2005