Euphnerins A and B, Diterpenoids with a 5/6/6 Rearranged Spirocyclic Carbon Skeleton from the Stems of Euphorbia neriifolia

Euphnerins A (1) and B (2), two extremely modified diterpenoids possessing an unprecedented 5/6/6 rearranged spirocyclic carbon skeleton, and a biosynthetically related known diterpenoid (3) were purified from the stems of Euphorbia neriifolia. Their structures were identified by NMR experiments and X-ray diffraction analysis, as well as experimental and calculated electronic circular dichroism data comparison. A putative biosynthetic relationship of 1 and 2 with their presumed precursor 3 is proposed. Compound 1 showed NO inhibitory effects in lipopolysaccharide-stimulated BV-2 cells with an IC50 value of 22.4 mu M.