Peptide-catalyzed asymmetric control of nitroalkane conjugate addition

ORGN 762

Brian R. Linton, blinton@bowdoin.edu1, Chris M. Aderman1, Catherine A. Evans, CEvans@ipi.com2, and Scott J. Miller, scott.miller@yale.edu3. (1) Department of Chemistry, Bowdoin College, Brunswick, ME 04011, (2) Department of Chemistry, Infinity Pharmaceuticals Inc, 780 Memorial Drive, Cambridge, MA 02139, (3) Department of Chemistry, Yale University, 225 Prospect Street, P. O. Box 208107, New Haven, CT 06520-8107
Conformationally-defined peptides have been used to catalyze the enantioselective Michael addition of nitrocarbonyl derivatives to vinyl ketones. Maximal selectivity was observed with peptides containing a combination of protected histidine and arginine residues spanning a beta turn. Subtle rearrangement of the functionality permits access to both stereoisomers with varying degrees of selectivity. Mechanistic investigation suggests preorganization on the peptide, followed by rate-determining nucleophilic attack.
 

Asymmetric Reactions, Molecular Recognition, Self Assembly, Bioorganic Chemistry, Process R&D
8:00 PM-10:00 PM, Wednesday, 16 March 2005 Convention Center -- Hall D, Poster

Division of Organic Chemistry

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