Gelsecorydines A-E, Five Gelsedine-Corynanthe-Type Bisindole Alkaloids from the Fruits of Gelsemium elegans.

Five monoterpenoid bisindole alkaloids with new carbon skeletons, gelsecorydines A-E (1-5), together with their biogenetic precursors were isolated from the fruits of Gelsemium elegans. Compounds 1-5 represent the first examples of heterodimeric frameworks composed of a gelsedine-type alkaloid and a modified corynanthe-type one. Notably, compound 2 featured an unprecedented caged skeleton with a 6/5/7/6/5/6 heterohexacyclic ring system, which possessed a pyridine ring that linked the two monomers. Their structures and absolute configurations were elucidated by spectroscopic analysis, X-ray diffraction, and electronic circular dichroism (ECD) calculation. A plausible biosynthetic pathway for compounds 1-5 is proposed. Compounds 1, 3, 4, and 5 exhibited a significant inhibitory effect against nitric oxide (NO) production in macrophages.