Abstract
An approach to synthesize the pentacyclic framework of the polyol diterpenoid ryanodol is reported. The ABC tricycle was constructed by a Co-mediated Pauson-Khand reaction, and both radical and anionic cyclization pathways were developed to form the E-ring. In addition, a reaction sequence involving SeO(2)-mediated enone oxidation and hydroxyl-directed oxy-Michael addition was developed to introduce the A-ring oxidation. The feasibility of forming the bridging D-ring by an oxidative dearomatization was established.