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A Synergistic Combinatorial and Chiroptical Study of Peptide Catalysts for Asymmetric Baeyer–Villiger Oxidation
Author(s) -
Giuliano Michael W.,
Lin ChungYon,
Romney David K.,
Miller Scott J.,
Anslyn Eric V.
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201500230
Subject(s) - chemistry , circular dichroism , baeyer–villiger oxidation , catalysis , combinatorial chemistry , monooxygenase , enantioselective synthesis , rational design , stereochemistry , organic chemistry , nanotechnology , enzyme , materials science , cytochrome p450
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.