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

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 15S 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-pi-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.

Automated summary

Two novel diterpenoids were isolated from Euphorbia helioscopia, with unique structures and biosynthetic pathways. Compound 1 exhibited potent immunosuppressive effect and inspired further study through biomimetic conversion research.