Lemnalemnanes A–C, Three Rare Rearranged Sesquiterpenoids from the Soft Corals Paralemnalia thyrsoides and Lemnalia sp.

Three novel sesquiterpenoids, lemnalemnanes A–C (1–3), were obtained from marine soft corals Paralemnalia thyrsoides and Lemnalia sp. Their structures were determined by 1D/2D NMR spectroscopy, HRESIMS, single-crystal X-ray diffraction analysis (Cu Kα), Mosher’s method, and ECD quantum chemistry calculations. Lemnalemnane A (1) possessed an intriguing basket-like structure with a spiro­[bicyclo[3.3.1]­nonane-furan core, while lemnalemnanes B (2) and C (3) exhibited unusual 6/6/5 and 6/5/5 carbon skeletons, respectively. In the proposed biosynthesis pathway, 1–3 were suspected to originate from the same precursor, 4-O-deacetylparalemnolin D (4), a compound coisolated from both aforementioned species. Furthermore, lemnalemnane C (3) exhibited strong in vivo promoting-angiogenesis activity.