A highly efficient and stereoselective route to potential synthetic intermediates for ocellenyne and related C₁₅ acetogenin natural products with 6,10-syn- and 6,10-anti-2,5-dioxabicyclo[2.2.1]heptane core structures has been developed by means of an iterative biogenesis-inspired oxonium ion formation/fragmentation sequence. In accordance with chemical transformations, the most likely stereostructure for (E)-ocellenyne on the basis of GIAO ¹³C NMR calculations possesses a 6,10-anti-2,5-dioxabicyclo[2.2.1]heptane core, as predicted from a plausible biosynthetic pathway, instead of the spectroscopically proposed 6,10-syn-2,5-dioxabicyclo[2.2.1]heptane skeleton.

中文翻译：

---

氧离子形成/断裂法构建6,10-顺式和反式-2,5-二氧杂双环[2.2.1]庚烷骨架：（E）-Ocellenyne结构的NMR预测

通过开发一种高效，立体选择性的途径，可开发出具有6,10-顺-和6,10-抗-2,5-二氧杂双环[2.2.1]庚烷核心结构的奥氏炔和相关的C _15产乙酸原天然产物的潜在合成中间体。迭代的生物发生启发式的氧离子形成/片段化序列的方法。根据化学转化，根据GIAO ¹³ C NMR计算，（E）-邻二炔的最可能的立体结构具有6,10-抗-2,5-二氧杂双环[2.2.1]庚烷核，从合理的生物合成途径，而不是光谱学上提出的6,10- syn-2，5-二氧杂双环[2.2.1]庚烷骨架。