title: A Synergistic Combinatorial and Chiroptical Study of Peptide Catalysts for Asymmetric Baeyer-Villiger Oxidation.
abstract: We report an approach to the asymmetric Baeyer-Villiger oxidation utilizing bioinformatics-inspired combinatorial screening for catalyst discovery. Scaled-up validation of our on-bead efforts with a circular dichroism-based assay of alcohols derived from the products of solution-phase reactions established the absolute configuration of lactone products; this assay proved equivalent to HPLC in its ability to evaluate catalyst performance, but was far superior in its speed of analysis. Further solution-phase screening of a focused library suggested a mode of asymmetric induction that draws distinct parallels with the mechanism of Baeyer-Villiger monooxygenases.
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, United States, ;
authors.forename: Michael W
authors.initials: MW
authors.lastname: Giuliano
authors.affiliation: Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States, ;
authors.forename: Chung-Yon
authors.initials: CY
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, United States, ;
authors.forename: David K
authors.initials: DK
authors.lastname: Romney
authors.affiliation: Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, United States, ;
authors.forename: Scott J
authors.initials: SJ
authors.lastname: Miller
authors.affiliation: Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States, ;
authors.forename: Eric V
authors.initials: EV
authors.lastname: Anslyn
keywords: Baeyer-Villiger oxidation; catalysis; circular dichroism; peptides