Peptide-catalyzed enantioselective cycloisomerizations in the Morita-Baylis-Hillman family

ORGN 28

Carrie E. Aroyan, aroyan@bc.edu, Department of Chemistry, Boston College, Merkert Chemistry Center, 2609 Beacon Street, Chestnut Hill, MA 02467 and Scott J. Miller, scott.miller@yale.edu, Department of Chemistry, Yale University, 225 Prospect Street, P. O. Box 208107, New Haven, CT 06520-8107.
The potential of the Morita-Baylis-Hillman (MBH) reaction to rapidly increase molecular complexity, while incorporating new stereogenic centers has been explored. The extension of the intramolecular cyclization to include alternative electrophilic partners, such as a Michael acceptor in the vinylogous variant, in an enantioselective manner, will be presented. Various nucleophilic catalysts have been examined and we found that simple amino acid derivatives were sufficiently active, promoting the enantioselective cycloisomerization of bisenones. Even single amino acids, in combination with the appropriate base, were found to be competent catalysts for this reaction and afforded the desired cyclized products with significant enantioselectivity. The effects of catalyst structure on yield and selectivity of the reaction will be discussed.

 

Asymmetric Reactions and Syntheses
8:00 AM-12:20 PM, Sunday, 10 September 2006 Moscone Center -- Room 131, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006