Highly Enantioselective, Organocatalytic, and Scalable Synthesis of a Rare cis,cis ‐Tricyclic Diterpenoid

A highly enantioselective, organocatalytic, and scalable synthesis of a very unusual cis ‐decalin‐ cis ‐hydrindane tricyclic diterpenoid system has been achieved. Despite the prevalent pharmacological space that the related trans , trans and trans , cis ‐systems occupy, there have been no reports of an asymmetric synthesis of the cis , cis systems in the literature until now. We demonstrate the flexibility of our approach not only through access to a diverse range of products, all of which are attained in exceptionally high selectivities, but also by showing their easy conversion to the corresponding trans , cis ‐system and other derivatives.