Synthesis of the All-l Cyclopentapeptides Versicoloritides A, B, and C

 

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Abstract

Herein we describe the first synthesis of the all-l naturally occurring cyclopentapeptides versicoloritides A, B, and C. We found that the extent of oligomerization and epimerization upon head-to-tail cyclization of the linear pentapeptide precursors could be reduced to acceptable levels by modifying the reaction conditions.

• References and Notes

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• 20 Versicoloritide C (3) To a solution of DIPEA (60 μL, 344 μmol) in CH₂Cl₂ (80 mL) was added 6 (40 mg, 67 μmol) and HBTU (77 mg, 200 μmol) in CH₂Cl₂–DMF (5:1, 22 mL) at 0.5 mL/h. After complete addition of the reagents, the reaction mixture was concentrated under reduced pressure, diluted with 0.1% TFA–H₂O (v/v, 18 mL), and purified by RP-HPLC to afford 3 as a colorless solid (17 mg, 44%). HRMS (EI): m/z [M + Na]⁺ calcd for C₃₁H₃₇N₅NaO₆: 598.2642; found: 598.2645. IR: 3307, 2956, 1632, 1523, 1443, 1345, 1165, 746, 700 cm^–1. [α]_D ²⁰ –135.5 (c 0.2, MeOH) [lit. –118 (c 0.2, MeOH)].¹ See Supporting Information for complete procedures and analytical data

• Supplementary Material