Total Synthesis of (+)‐Daphmanidin E

From ring to ring: The first total synthesis of (+)-daphmanidin E features rapid access to an enantiomerically pure bicyclo[2.2.2]octadione and elaboration around its periphery through the implementation of two Claisen rearrangements, the use of a copper/peptide complex for reagent-controlled stereoselective conjugate addition, a diastereoselective hydroboration, and a cobalt-catalyzed alkyl-Heck cyclization.