Four geranyl-bearing polyisoprenylated benzoylphloroglucinol derivatives from Hypericum sampsonii

► Non-polar novel acylphloroglucinol natural products were isolated from Hypericum sampsonii. ► Structures were assigned on the basis of NMR spectroscopy, mass spectrometry and crystal X-ray structural analysis. ► These compounds possessed unusual adamantane-like cage structures. ► Structures highlight the potential of the genus Hypericum to produce distinct, highly functional and chiral natural products.