Total Synthesis of (−)-Dolastatrienol

The first asymmetric total synthesis of the tricyclic diterpenoid natural product (−)‐dolastatrienol has been accomplished using a rhodium(II)‐catalyzed carbene cyclization cycloaddition cascade reaction as the key step to construct the [5.4.0]carbobicyclic core. An intramolecular Heck reaction furnished the tricyclic skeleton and a challenging methylenation completed the synthesis of the target. Her name was Dola, she was a statrienol: The asymmetric total synthesis of the diterpenoid (−)‐dolastatrienol has been accomplished using a rhodium(II)‐catalyzed carbene cyclization cycloaddition cascade reaction and an intramolecular Heck reaction as the key steps to furnish the tricyclic skeleton.