Isolation and Synthesis of Azuriaplysins A and B, Bromoditerpenes with an α‑Methylene Carbonyl from the Sea Hare <i>Aplysia kurodai</i>

New bromoditerpenes having an α-methylene carbonyl structure, azuriaplysins A (1) and B (2), were isolated from the sea hare Aplysia kurodai. Their relative stereostructures were determined based on one- and two-dimensional NMR spectroscopic analysis. In addition, the absolute stereostructures were determined by the total synthesis of both enantiomers of azuriaplysins A (1) and B (2), the key points of which were bromocyclization of farnesol and optical resolution of a key intermediate. Azuriaplysin B (2) and its enantiomer exhibited moderate cytotoxicity against HeLa S3 cells.