Identification and synthesis of three cyclodidepsipeptides as potential precursors of enniatin B in Fusarium sporotrichioides

Abstract

A pathogenic fungus, Fusarium sporotrichioides Sherb., was isolated from Hypericum barbatum Jacq. The volatile compounds of broth and mycelium were analyzed using GC–MS and three cyclodidepsipeptides (dioxomorpholines), 3,6-di(propan-2-yl)-4-methyl-morpholine-2,5-dione, 3-(2-methylpropyl)-6-(propan-2-yl)-4-methyl-morpholine-2,5-dione and 3-(butan-2-yl)-6-(propan-2-yl)-4-methyl-morpholine-2,5-dione, were found for the first time in the natural products. The structures of the compounds were confirmed by comparison of the analytical data for the natural products with samples obtained via synthetic methods. The conformational features and vibrational spectra of the three cyclodidepsipeptides were characterized by density functional theory (DFT) calculations and IR spectroscopy. The cyclic hexadepsipeptide enniatin B was identified by a LC–MS/MS analysis of the non-volatile products of broth and mycelium. The above-mentioned three cyclodidepsipeptides are probably synthesized using similar biosynthetic ways to enniatin B involving a nonribosomal mechanism.