The synthesis of a natural product family: from debromoisolaurinterol to the aplysins

Total syntheses of (±)-aplysin 1, (±)-debromoaplysin 2, (±)-isoaplysin 3, (±)-aplysinol 4, (±)-debromoaplysinol 5, (±)-aplysinal 6, (±)-isolaurinterol 7 and (±)-debromoisolaurinterol 8 are described. Key features are a diastereoselective, sulfur mediated radical cyclisation of diene 12 to give 35; a new radical to polar crossover sequence mediated by Bu3Snradical dot that transforms diene 12 into (±)-debromoisolaurinterol 8; and a series of biomimetic cyclisation and oxidation reactions.