Unexpected Metabolic Versatility in a Combined Fungal Fomannoxin/Vibralactone Biosynthesis.
Unexpected Metabolic Versatility in a Combined Fungal Fomannoxin/Vibralactone Biosynthesis.
复制标题
DOI：
10.1021/acs.jnatprod.6b00147
复制
发表时间：
2016-04
影响因子：
5.1
通讯作者：
D. Schwenk;P. Brandt;R. Blanchette;M. Nett;D. Hoffmeister
中科院分区：
文献类型：
--
作者：
D. Schwenk;P. Brandt;R. Blanchette;M. Nett;D. Hoffmeister
研究了未描述的立体担子菌 (BY1) 的次级代谢组中的生物活性化合物。除了一种已知的福马诺辛衍生物和两种已知的振动内酯外，我们在这里描述了这些天然产物家族的三种新化合物，其结构是使用一维和二维核磁共振波谱和高分辨率质谱法阐明的。新化合物vibralactone S (4)显示出3,6-取代的oxepin-2(7H)-one环系统，这对于vibralactone/fomannoxin类化合物来说是前所未有的。稳定同位素标记建立了一种生物合成途径，该途径与已发表的两个奥塞平酮形成级联不同。另一种新化合物，抗真菌药物 seco-fomannoxinate (6)，具有 2-甲基丙-1-烯基醚部分，这在天然产物中很少观察到。通过全合成确认了6的结构。 (13)C标记实验表明，不寻常的2-甲基丙-1-烯基醚残基源自异戊二烯单元。 BY1 的福马诺辛/振动内酯组合代谢的多样性是显着的，因为这些化合物家族虽然生物合成相关，但通常出现在不同的生物体中。
The secondary metabolome of an undescribed stereaceous basidiomycete (BY1) was investigated for bioactive compounds. Along with a known fomannoxin derivative and two known vibralactones, we here describe three new compounds of these natural product families, whose structures were elucidated using 1D and 2D NMR spectroscopy and high-resolution mass spectrometry. The new compound vibralactone S (4) shows a 3,6-substituted oxepin-2(7H)-one ring system, which is unprecedented for the vibralactone/fomannoxin class of compounds. Stable isotope labeling established a biosynthetic route that is dissimilar to the two published cascades of oxepinone formation. Another new compound, the antifungal methyl seco-fomannoxinate (6), features a 2-methylprop-1-enyl ether moiety, which is only rarely observed with natural products. The structure of 6 was confirmed by total synthesis. (13)C-labeling experiments revealed that the unusual 2-methylprop-1-enyl ether residue derives from an isoprene unit. The diversity of BY1's combined fomannoxin/vibralactone metabolism is remarkable in that these compound families, although biosynthetically related, usually occur in different organisms.