Total Synthesis of the Meroterpenoid Manginoid A as Fueled by a Challenging Pinacol Coupling and Bicycle‐forming Etherification

The manginoids are a unique collection of bioactive natural products whose structures fuse an oxa‐bridged spirocyclohexanedione with a heavily substituted trans‐hydrindane framework. Herein, we show that such architectures can be accessed through a strategy combining a challenging pinacol coupling and bicycle‐forming etherification with several additional chemo‐ and regioselective reactions. The success of these key events proved to be highly substrate and condition specific, affording insights for their application to other targets. As a result, not only has a 19‐step total synthesis of manginoid A been achieved, but a potential roadmap to access other members of the family and related natural products has also been identified.