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Diterpenoids with Rearranged 9(10→11)- abeo -10,12-Cyclojatrophane Skeleton and the First (15 S )-Jatrophane from Euphorbia helioscopia : Structural Elucidation, Biomimetic Conversion, and Their Immunosuppressive Effects.

Zhi-Nan XiangQi-Lin TongJun-Cheng SuZhuo-Fan HuNing ZhaoRu-Feng XiaJia-Le WuChen ChenJia-Chun ChenLuo-Sheng Wan
Published in: Organic letters (2021)
Two novel diterpenoids, one with a rearranged trans , trans -fused tricyclo[10.3.0.0 4,6 ]pentadecane framework ( 1 ) and the other with an unprecedented 15 S configuration ( 2 ), were isolated from Euphorbia helioscopia . Their structures were elucidated by extensive analysis of HR-ESI-MS, NMR, quantum-chemical calculation, and X-ray crystallographic data. Biosynthetically, 1 has a unique "cyclopropane-shift-like" biogenesis involving an oxa-di-π-methane (ODPM) rearrangement, which inspired us to accomplish the biomimetic conversion of 3 to 1 . Moreover, compound 1 displayed a potent immunosuppressive effect by inhibiting Kv1.3 voltage-gated channels.
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