Portimine B was isolated from an extract derived from the dinoflagellate Vulcanodinium rugosum, a known producer of the closely related portimine A. Initial molecular characterization studies of portimine B suggested an open tetrahydrofuranyl ring isomer, contrary to the intact ring moiety found in portimine A. In 2023, the Baran lab synthesized both portimines A and B suggesting that both macrocyclic analogs contained the intact tetrahydrofuranyl ring. In this note, we utilize newly acquired NMR data, the i-HMBC NMR experiment, and advanced density functional theory calculations to define the structural divergence, originating from the presence of a transient hydrate.