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 Diels–Alder reaction,
a Pd-catalyzed O→C allylic rearrangement, a chemoselective
Wacker oxidation, and a Dieckmann condensation/hemiketalization cascade.