Total synthesis and structure elucidation of JBIR-39: A linear hexapeptide possessing piperazic acid and γ-hydroxypiperazic acid residues

Masahito Yoshida, Naoki Sekioka, Miho Izumikawa, Ikuko Kozone, Motoki Takagi, Kazuo Shin-ya, Takayuki Doi

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

Abstract

The total synthesis and stereochemical structural elucidation of JBIR-39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)3-catalyzed acylation of a Piz(γ-OTBS) derivative with piperazic acid chloride, providing the desired Piz-Piz(γ-OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)-isoleucic acid at the N-terminus, amidation with the (R)-α-methylserine ester at the C-terminus, and deprotection afforded the desired (2R,8S)-hexapeptide, which is the assumed structure of JBIR-39. Although the spectral data of the (2R,8 S)-hexapeptide was not identical to JBIR-39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR- 39 to be (2S,6S,8S,11 R,16S,21R,26S,27S).

Original languageEnglish
Pages (from-to)3031-3041
Number of pages11
JournalChemistry - A European Journal
Volume21
Issue number7
DOIs
Publication statusPublished - 2015 Feb 9

Keywords

  • Acylation
  • Configuration determination
  • Natural products
  • Peptides
  • Total synthesis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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