The total synthesis of complex natural products provides a unique opportunity for learning new lessons in chemical reactivity, which drives the field of synthesis forward. With this goal in mind, we describe our synthetic approach to (±)-amathaspiramide F, a polycyclic alkaloid. The key transformation in our strategy is a tandem palladium-catalyzed allylic amination/[2,3]-Stevens rearrangement, which was recently developed by our lab. Although our retrosynthetic analysis for the amathaspiramides was at first glance straightforward, we uncovered an unusual stereochemical effect that led us down an unexpected path to eventually solve the problem and complete the synthesis of amathaspiramide F. The unexpected diastereoselectivity of the [2,3]-Stevens rearrangement was controlled by the substitution patterns of an aromatic ring. This stereochemical switch may represent a new stereocontrolling element for [2,3]-sigmatropic rearrangements in complex molecular settings.