(±)-Caryopterisines A (1) and B (2) featuring an unprecedented 6/5/5/5/6 pentacyclic rings system were isolated from Caryopteris glutinosa. The structures were determined by spectroscopic and X-ray crystallographic data analyses as well as theoretical calculations. Chiral HPLC resolution of both racemic 1 and 2 afforded their corresponding enantiotropic enantiomers. A plausible biogenesis for 1 and 2 may be originated from Diels-Alder reaction between pyridine-containing oxerine derivatives. The enantiotropic conversion mechanism of the enantiomers was demonstrated by H-D exchange and 18O incorporation studies. Compounds 1 and 2 showed moderate inhibition of estrogen E2 biosynthesis in human ovarian granulosa-like KGN cells. These two alkaloids reduced kynurenine biosynthesis at moderate level via inhibition of indoleamine 2,3-dioxygenase. Alkaloid 2 exhibited moderate inhibition of the release of interleukin-1β.