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

Org Lett. 2018 Mar 16;20(6):1621-1625. doi: 10.1021/acs.orglett.8b00364. Epub 2018 Mar 5.

Abstract

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.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Cycloaddition Reaction
  • Disulfides
  • Molecular Structure
  • Peptides / chemistry*
  • Stereoisomerism

Substances

  • Disulfides
  • Peptides