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 S N 2' 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 .