Disulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis
journal contributionposted on 05.03.2018, 13:43 authored by Jonathan M. Ryss, Amanda K. Turek, Scott J. Miller
An enantioselective vinylcyclopropane ring-opening/cycloaddition cascade is described. The active thiyl radical catalysts are generated in situ via UV light-promoted homolysis of cystine-based dimers. Amide-functionalization of the peptide at the 4-proline position is essential for effective asymmetric induction. Stereochemical communication is dependent on steric interactions with this substituent that are enforced by H-bonding to the peptide backbone.
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Disulfide-Bridged PeptidesMediate Enantioselective CycloadditionsStereochemical communicationUV light-promoted homolysisring-openingenantioselectiveH-bondingThiyl Radical Catalysissubstituentpeptide backbonecystine-based dimers4- proline positioncatalystthiylAmide-functionalizationinductionsteric interactionscascadevinylcyclopropane