The marine-derived fungus Trichoderma sp. TPU199 (cf. Trichoderma brevicompactum) produces pretrichodermamide A (1) and gliovirin (2), which possess a rare type of epipolythiodiketopiperazine (ETP) structure with a disulfide bridge between the α- and β-positions of two amino acid residues. We previously reported that this strain gave the halogenated ETPs, DC1149B (4), DC1149R (6), and iododithiobrevamide (7), when fermented with sodium halides (NaCl, NaBr, and NaI). Further analyses of the metabolites obtained under NaI-containing culture conditions resulted in the isolation of two new ETP derivatives (11 and 12) and three new trichothecene sesquiterpenes (13-15). The structures of 11 and 12, including their absolute configurations, were elucidated based on spectroscopic data for 11 and 12 and comparisons with those for 1 and related compounds, revealing that 11 was an epimer of 1 at the C-5 position and 12 was a trithio-derivative of 11. The structures of 13-15 were established by analyzing their 1D and 2D NMR data. The absolute configurations of 13-15 were assigned by comparing their experimental electronic circular dichroism (ECD) spectra with the calculated ECD spectrum of 13.

中文翻译：

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来自海洋衍生木霉的含NaI发酵的Epipolythiodiketopiperazine和trichothecene衍生物cf. brevicompactum。

海洋来源的真菌木霉属。TPU199（参见短小木霉）生产前trichodermamide A（1）和gliovirin（2），它们具有罕见类型的表聚硫代二酮哌嗪（ETP）结构，在两个氨基酸残基的α和β位之间具有二硫键。我们先前曾报道，当用卤化钠（NaCl，NaBr和NaI）发酵时，该菌株产生了卤代ETP，DC1149B（4），DC1149R（6）和碘二硫代乙酰胺（7）。在含NaI的培养条件下获得的代谢物的进一步分析导致分离出两种新的ETP衍生物（11和12）和三种新的单端孢子烯倍半萜（13-15）。根据11和12的光谱数据并与1和相关化合物的光谱数据进行比较，阐明了11和12的结构，包括其绝对构型，揭示11是C-5位置的差向异构体，12是11的三硫键衍生物。通过分析1D和2D NMR数据，确定13-15的结构。通过比较13-15的实验电子圆二色性（ECD）光谱与计算出的13的ECD光谱来确定13-15的绝对构型。