College of Pharmacy, Seoul National University , Seoul 08826, Korea.
Chemical Research Laboratory, Department of Chemistry, University of Oxford , Mansfield Road, Oxford OX1 3TA, U.K.
Org Lett. 2017 Nov 17;19(22):6252-6255. doi: 10.1021/acs.orglett.7b03226. Epub 2017 Nov 7.
A highly efficient and stereoselective route to potential synthetic intermediates for ocellenyne and related C 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 C 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.
已开发出一种高效和对映选择性的方法，用于合成潜在的奥塞林恩和相关 C 型乙酰氧基天然产物的合成中间体，这些中间体具有 6,10-顺式和 6,10-反式-2,5-二氧杂双环[2.2.1]庚烷核心结构，采用迭代生物发生启发的氧鎓离子形成/断裂序列。根据化学转化，基于 GIAO C NMR 计算，（E）-奥塞林恩最有可能的立体结构具有 6,10-反式-2,5-二氧杂双环[2.2.1]庚烷核心，这与从合理的生物合成途径预测的一致，而不是光谱上提出的 6,10-顺式-2,5-二氧杂双环[2.2.1]庚烷骨架。
