The total synthesis of eleutherobin

The total synthesis of the title compound (1), starting with (R)-(-)-alpha-phellandrene (6), has been accomplished. The synthesis rigorously proves the relative stereochemical relationship of the diterpenoid and carbohydrate domains of eleutherobin. Key reactions included a Nozaki-Kishi ring closure to produce a furanophane (see 37 --> 38), a pyranose to furanose transposition (see 50 --> 47), and a novel oxycarbaglycosidation (cf. 58 --> 87) for joining the two domains.