Total Synthesis of (−)‐Ulapualide A: The Danger of Overdependence on NMR Spectroscopy in Assignment of Stereochemistry

Lessons learnt: The asymmetric total synthesis of the macrolide (−)-ulapualide A has been accomplished. Interestingly, the 1H NMR spectrum and chiroptical data of the macrolide and of a previously synthesized diastereoisomer with opposite stereocenters at C3, C28, C29, C30, and C32 were superimposable, which highlights the care that must be taken in the assignment of configurations to complex structures based on NMR spectroscopy.