Oral Presentation 6th Modern Solid Phase Peptide Synthesis & Its Applications Symposium 2017

3-Nitro-2-pyridinesulfenyl resin-mediated solid-phase disulfide ligation for the synthesis of cyclic peptides and peptide-drug conjugates (#33)

Yoshio Hayashi 1
  1. Tokyo University of Pharmacy and Life Sciences, Hachioji, Tokyo, Japan

With an emphasis on our studies focused on 3-nitro-2-pyridinesulfenyl (Npys) unit,1,2 we report herein a new “two step solid-phase disulfide ligation” method. This is a strategy to prepare a disulfide peptide from two different peptide fragments containing cysteine residues.3 Briefly, a peptide fragment A containing Cys(t-Bu) is loaded onto Npys chloride resin via the formation of an active disulfide bond. The resulting resin-attached peptide A is then readily transferred to another Cys-containing peptide fragment B by a disulfide exchange reaction, selectively forming and releasing the new disulfide peptide C from the resin. Peptide C is easily recovered in high purity by filtration. Subsequent amide bond formation yields the desired cyclic peptide. This strategy sets up a novel disulfide-led synthetic methodology for disulfide-containing cyclic peptides. During the presentation, the syntheses of cyclic peptides, oxytocin and endothelin will be discussed as a fundamental model towards more complex cyclic peptides. As another application, since a notable difference in solubility between hydrophilic biocompatible carriers and hydrophobic small-molecule drugs makes their chemical conjugation difficult, particularly in peptide–drug conjugation, we adopted the above-mentioned two-step solid-phase disulfide ligation.4 Suitable solvent systems can be used for reactant solubilization during each step. Hydrophobic antitumor agent plinabulin5 and hydrophilic octaarginine were successfully conjugated via disulfide bond as a practical model.

  1. Fukumoto, K., Hayashi, Y. et al., Tetrahedron Lett., 2012, 53, 535.
  2. Fukumoto, K., Hayashi, Y. et al., Asian J. Org. Chem., 2015, 4,1030.
  3. Taguchi, A., Hayashi, Y. et al., Org. Biomol. Chem., 2015, 13, 3186.
  4. Muguruma, K., Hayashi, Y. et al., Bioconjugate Chem., 2016, 27, 1606.
  5. Yamazaki, Y., Hayashi, Y. et al., J. Med. Chem., 2012, 55, 1056.