Total Synthesis of the Alleged Structure of (+)-Fimbricalyxoid A

An enantioselective total synthesis of the alleged structure of (+)-fimbricalyxoid A is reported. The synthetic strategy features a pyridine-N-oxidate-mediated SN2′ reaction to introduce an oxygen functionality at position C3 of the A-ring and a sequential three-step process via the cleavage of the C–O bonds and hemiketalization to form the 3,20-oxybridge. With this strategy, the target molecule was synthesized in 19% overall yield and 12 steps from our previously synthesized cis-fused octahydrophenanthrene (+)-6.