Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
Institut für Organische Chemie, TU Braunschweig, Hagenring 30, 38106 Braunschweig (Germany).
Angew Chem Int Ed Engl. 2015 May 26;54(22):6637-40. doi: 10.1002/anie.201501765. Epub 2015 Apr 15.
Feeding of (2,3,4,5,6-(13) C5 )mevalonolactone to the fungus Hypomyces odoratus resulted in a completely labeled sesquiterpene ether. The connectivity of the carbon atoms was easily deduced from a (13) C,(13) C COSY spectrum, revealing a structure that was different from the previously reported structure of hypodoratoxide, even though the reported (13) C NMR data matched. A structural revision of hypodoratoxide is thus presented. Its absolute configuration was tentatively assigned from its co-metabolite cis-dihydroagarofuran. Its biosynthesis was investigated by feeding of (3-(13) C)- and (4,6-(13) C2 )mevalonolactone, which gave insights into the complex rearrangement of the carbon skeleton during terpene cyclization by analysis of the (13) C,(13) C couplings.
（2,3,4,5,6-(13)C5）甲羟戊酸内酯喂养真菌Hypomyces odoratus 导致完全标记的倍半萜醚。通过（13）C,（13）C COSY 光谱很容易推断出碳原子的连接性，揭示了一种与先前报道的hypodoratoxide 结构不同的结构，尽管报道的（13）C NMR 数据相匹配。因此，提出了 hypodoratoxide 的结构修订。其绝对构型是根据其共代谢物顺式二氢agarofuran 来推测的。通过喂养（3-(13)C）-和（4,6-(13)C2）甲羟戊酸内酯研究了其生物合成，通过分析（13）C,（13）C 偶合，深入了解了萜类环化过程中碳骨架的复杂重排。
