title: Peptide-catalyzed conversion of racemic oxazol-5(4H)-ones into enantiomerically enriched α-amino acid derivatives.
abstract: We report the development and optimization of a tetrapeptide that catalyzes the methanolytic dynamic kinetic resolution of oxazol-5(4H)-ones (azlactones) with high levels of enantioinduction. Oxazolones possessing benzylic-type substituents were found to perform better than others, providing methyl ester products in 88:12 to 98:2 er. The mechanism of this peptide-catalyzed process was investigated through truncation studies and competition experiments. High-field NOESY analysis was performed to elucidate the solution-phase structure of the peptide, and we present a plausible model for catalysis.
authors: Department of Chemistry, Yale University , New Haven, Connecticut 06520-8107, United States.
authors: Anthony J
authors: AJ
authors: Metrano
authors: Scott J
authors: SJ
authors: Miller
mesh_terms: D000596:Amino Acids / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010080:Oxazoles / Q000737:chemistry*; D010081:Oxazolone / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000596:Amino Acids; D010080:Oxazoles; D010455:Peptides; D010081:Oxazolone