Enantioselective total synthesis of (+)-pedrolide | Poster Board #3410

The first total synthesis of (+)-pedrolide, a rearranged tigliane-type diterpenoid featuring an unprecedented pentacyclic carbon skeleton, is reported. Key to the approach is the construction of the embedded bicyclo[2.2.1]heptane via an intramolecular cyclopentadiene-Diels–Alder reaction. To this end, a norbornadiene serves as an effective surrogate for cyclopentadiene, which is unmasked under mild conditions involving a complex Diels–Alder reaction cascade. In addition, the synthesis provides a novel and efficient approach to a highly functionalized carane in an enantioselective manner.