Convergent Total Syntheses of (−)‐Rubriflordilactone B and (−)‐ pseudo ‐Rubriflordilactone B

A highly convergent strategy for the synthesis of the natural product (−)‐rubriflordilactone B, and the proposed structure of (−)‐ pseudo ‐rubriflordilactone B, is described. Late stage coupling of diynes containing the respective natural product FG rings with a common AB ring aldehyde precedes rhodium‐catalyzed [2+2+2] alkyne cyclotrimerization to form the natural product skeleton, with the syntheses completed in just one further operation. This work resolves the uncertainty surrounding the identity of pseudo ‐rubriflordilactone B and provides a robust platform for further synthetic and biological investigations.