Hyperacmosins K-M, three new polycyclic polyprenylated acylphloroglucinols from Hypericum acmosepalum

Hyperacmosins K-M (1-3), three new polycyclic polyprenylated acylphloroglucinol (PPAPs) derivatives, were isolated from the air-dried aerial parts of Hypericum asmosepalum. Compounds 1 and 2 both possessed a rare 5,5-spiroketal subunit with the loss of C-2' carbonyl in the phloroglucinal ring, while compound 3 featured an unusual 1,2-seco-bicyclo[3.3.1] PPAP skeleton. Their structures were confirmed by NMR, HRESIMS, and CD spectra. The plausible biogenetic pathways of 1-3 were proposed, which gave an insight for future biomimetic synthesis of the novel compounds.