Reassignment of improbable natural products identified through chemical principle screening

Natural products continue to be reported at an astonishing rate from a wide range of multidisciplinary research activities in the pursuit of understanding the chemistry of biodiversity. However, the elucidation of chemical structure in the modern era is heavily reliant on the analysis and interpretation of multiple spectroscopic outputs, and in most cases this activity is by no means trivial. Structural errors continue to be described given the inherent complexity of natural products. Computer-Assisted Structure Elucidation (CASE) continues to provide improved resolving power in this regard, but for enhanced accuracy quantum chemical spectrum prediction methodology is paramount. Reported herein are a range of counterfactual natural products, identified through chemical principal screening, which have been reassigned using a combination of chemical intuition, chemical synthesis, CASE and DU8+ spectrum prediction.Nanyang Technological UniversityPublished versionWe thank the University of Denver, the University of Queensland and Nanyang Technological University for financial support, along with Advanced Chemistry Development, Inc. (ACDLabs). The Australian Research Council for funding to C.M.W. (FT110100851). A.G.K. thanks the US National Science Foundation (CHE‐1955892) for support