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Synthesis of Cyclophane-Braced Peptide Macrocycles via Palladium-Catalyzed Intramolecular C(sp3)-H Arylation of N-Methyl Alanine at C-Termini.

Xinghua LiLiping QiBo LiZhenxiang ZhaoGang HeGong Chen
Published in: Organic letters (2020)
A method for the construction of cyclophane-braced peptide macrocycles via Pd-catalyzed aminoquinoline-directed intramolecular C(sp3)-H arylation with aryl iodides is developed. Unlike our previous AQ-directed exo-type intramolecular C-H arylation of long alkyl tails, this endo-type C-H cyclization reaction takes places on the β-methyl group of N-methyl alanine at the C-termini of peptides. Unusual C-N cleavage side products of Ala were observed and attributed to intramolecular deprotonation-assisted α,β-elimination of the palladacycle intermediate.
Keyphrases
  • energy transfer
  • ionic liquid
  • quantum dots
  • amino acid