Founding Strategic Bases for the Total Synthesis of Naphthocyclinones: Design and Preparation of an Acceptor Unit and Stereoselective Construction of the Bicyclic Framework

Abstract Synthetic study on the naphthocyclinones is described, focusing on the design of a viable acceptor unit for 1,4-addition to develop feasible synthetic routes. Valuable insights have been uncovered, concerning the unique reactivity of hydroquinone and the photo-lability of naphthoquinone during their preparation. Furthermore, the acceptor unit was employed for studying the construction of the bicyclo[3.2.1]octadienone core by the planned key reactions, Rh-mediated stereoselective 1,4-addition and thiolate-mediated reductive cyclization. The knowledge provided a firm basis for our preceding total synthesis that was recently reported.