Institut für Organische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany.
Chembiochem. 2011 Sep 5;12(13):2088-95. doi: 10.1002/cbic.201100268. Epub 2011 Jul 11.
The volatiles of the fungus Fusarium verticillioides were analysed by GC-MS. Sesquiterpenes dominated, with trichodiene as the principle component. Several other sesquiterpenes were detected in low amounts that were unambiguously identified from their mass spectra and retention indices. The absolute configurations of (R)-β-bisabolene, (R)-cuparene, (+)-β-barbatene, (-)-α-cedrene, (+)-β-cedrene, and (+)-α-funebrene originating from different key cationic intermediates, were determined by chiral GC-MS and proved to be related to the trichodiene stereostructure. The unusual compound (E)-iso-γ-bisabolene was also found corroborating a previously suggested mechanism for the cyclisation of the bisabolyl to the cuprenyl cation that is based on quantum mechanical calculations (Y. J. Hong, D. J. Tantillo, Org. Lett. 2006, 8, 4601-4604). These analyses resulted in a revised biosynthesis scheme to trichodiene and the side products of the responsible terpene cyclase, trichodiene synthase, an enzyme that is well characterised from Fusarium sporotrichioides. Feeding studies with several deuterated mevalonolactone isotopomers unravelled stereochemical aspects of the late cyclisations towards trichodiene.
通过 GC-MS 对镰刀菌挥发性物质进行了分析。倍半萜类物质占主导地位，以曲霉菌为主要成分。还检测到几种低含量的其他倍半萜类物质，它们的质谱和保留指数明确表明了其身份。来自不同关键阳离子中间体的（R）-β-双醇、（R）-库柏烯、（+）-β-巴塔烯、（-）-α-雪松烯、（+）-β-雪松烯和（+）-α-芬尼烯的绝对构型通过手性 GC-MS 确定，并证明与曲霉菌的立体结构有关。还发现了不寻常的化合物（E）-异-γ-双醇，这也证实了之前基于量子力学计算提出的双醇环化形成库柏烯阳离子的环化机制（Y. J. Hong，D. J. Tantillo，Org. Lett. 2006, 8, 4601-4604）。这些分析结果导致对曲霉菌和负责萜烯环化酶（曲霉菌合成酶）的侧产物的生物合成方案进行了修订，该酶已从深绿木霉中得到很好的描述。用几种氘代甲羟戊酸内酯同位素进行的喂养研究揭示了曲霉菌晚期环化的立体化学方面。
