Biomimetic asymmetric total synthesis of (-)-laurefucin via an organoselenium-mediated intramolecular hydroxyetherification.

The first asymmetric total synthesis of (−)-laurefucin (1), a unique C-15 acetogenin with a 2,8-dioxabicyclo[5.2.1]decane skeleton, has been accomplished in nine steps in 31% overall yield from known oxocene 10. Highlights of the highly stereoselective synthesis include a novel organoselenium-mediated biomimetic hydroxyetherification.