Aphapolin A, a nemoralisin‐type diterpenoid possessing a unique 4/5‐fused‐ring system that is unprecedented in previously reported nemoralisin diterpenoid, and aphapolin B, a novel nemoralisin‐type diterpenoid derivative containing a benzofuran moiety, along with a new natural product were isolated from Aphanamixis polystachya (Wall.) R. Parker. Their structures and absolute configurations were elucidated by spectroscopy data, X‐ray crystallography diffraction analysis, and electronic circular dichroism calculations. Plausible biosynthetic pathways of aphapolins A and B were also delineated.
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