Disulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis

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 asymmet...

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Bibliographic Details
Published in:Organic letters 2018-03, Vol.20 (6), p.1621-1625
Main Authors: Ryss, Jonathan M, Turek, Amanda K, Miller, Scott J
Format: Article
Language:English
Subjects:
Catalysis
Cycloaddition Reaction
Disulfides
Molecular Structure
Peptides - chemistry
Stereoisomerism
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Summary: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.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.8b00364