Reassignment of the structures of pestalopyrones A–D.

Pestalopyrones A–D are four unusual tricyclic pyrone derivatives with flexible chiral structures, isolated from the endophytic fungus Pestalotiopsis neglecta S3. The full elucidation of their structures was a challenging task, and remained unsolved in the original article. Herein, the relative configurations of pestalopyrones A and pestalopyrones B were unambiguously assigned by detailed analyses on spectroscopic data and GIAO 13C NMR calculation method with sorted training sets (STS). The planar structures of pestalopyrones C and pestalopyrones D were revised by reinterpretation of their reported spectroscopic data, and then their relative configurations were deduced by STS GIAO 13C NMR calculation and NOE analysis. The absolute configurations of all the mentioned compounds were determined by the comparison of their experimental and calculated ECD curves. [Display omitted] • The planar structures of pestalopyrones C and D were revised. • Relative configuration determined by 13C NMR calculation and NOE analysis. • The absolute configurations were elucidated by ECD calculation. [ABSTRACT FROM AUTHOR]