Total Synthesis of (-)-Fusarisetin A and Reassignment of the Absolute Configuration of Its Natural Counterpart

The first total synthesis of (-)-fusarisetin A, the enantiomer of naturally occurring acinar morphogenesis inhibitor (+)-fusarisetin A, was accomplished in 13 steps, leading to the reassignment of the absolute configuration of the natural product. The synthesis featured a Lewis acid-promoted intramolecular Diets-Alder reaction, a Pd-catalyzed O -> C allylic rearrangement, a chemoselective Wacker oxidation, and a Dieckmann condensation/hemiketalization cascade.