Gloriosaols A and B, two novel phenolics from Yucca gloriosa: structural characterization and configurational assignment by a combined NMR-quantum mechanical strategy

Abstract Gloriosaols A ( 1 ) and B ( 2 ), two novel phenolic derivatives characterized by unusual spirostructures made up of two C 15 units linked via a γ-lactone to a central stilbenic portion were isolated from the roots of Yucca gloriosa . On the basis of an extensive NMR analysis, the same basic structure was established for the two compounds but no further information about their structural difference could be deduced. Thus two hypotheses were formulated: (1) gloriosaols A and B could be atropisomers caused by a restriction of the free rotation around the double bond due to a steric congestion of the bulky phenolic portions; (2) gloriosaols A and B could be two configurational isomers, indicating, in this case, a nonstereoselective biogenetic formation of the stereogenic center C-2. Semi-empirical calculations of the potential energy surfaces on gloriosaols A and B, together with the 1 H NMR spectra recorded at various temperatures, allowed us to unambiguously exclude the hypothesis of two restricted rotational conformers of a single configurational isomer. Finally, quantum mechanical calculations of the geometries and of the 1 H chemical shifts on the gloriasols A and B in combination with the analysis of the ROE data allowed us to deduce a diastereomeric relation between the two compounds and to assess the relative configuration of the two diastereomers.