(±)-Ganoapplanin, a Pair of Polycyclic Meroterpenoid Enantiomers from Ganoderma applanatum

(±)-Ganoapplanin (1), a pair of novel meroterpenoid enantiomers featuring an unprecedented dioxaspirocyclic skeleton constructed from a 6/6/6/6 tetracyclic system and an unusual tricyclo[4.3.3.0^3',7']dodecane motif, were isolated from Ganoderma applanatum. Its structure and absolute configurations were determined by spectroscopic analyses, X-ray crystallography, and ECD (electronic circular dichroism calculations). A plausible biogenetic pathway, involving a key Gomberg-Bachmann reaction, was also proposed for (±)-1. Biological studies showed that (±)-1 and its enantiomers exhibited different inhibitory activities on T-type voltage-gated calcium channels.