Total Synthesis of ent-Plagiochianin B.

An enantioselective total synthesis of plagiochianin B is described that employs (+)-3-carene as its point of departure and delivers the enantiomer of the natural product. Key features of the synthesis include a palladium-mediated regioselective oxidative cleavage of an olefin residing on a pyridine derived from a 6π-azatriene electrocyclization.