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The absolute configuration of the sesquiterpenoid plant and fungal phytotoxins inuloxin A (1) and seiricardine A (2) was obtained by the concerted application of ECD, ORD, and VCD methodologies. Seiricardine A needed to be converted in the corresponding 2-O-p-Br-benzoate ester (3). [Display omitted]
•Absolute configuration assignment by chiroptical methods.•Fungal and plant sesquiterpenoid phytotoxins.•Application of more than a single chiroptical methodology.•Application of ECD and ORD methodologies also to UV–Vis transparent molecules.
The absolute configuration (AC) of the plant phytotoxin inuloxin A, produced by Inula viscosa, and of the fungal phytotoxin seiricardine A, obtained from Seiridium fungi, pathogen for cypress, has been determined by experimental measurements and theoretical simulations of chiroptical properties of three related methods, namely, Optical Rotatory Dispersion (ORD), Electronic Circular Dichroism (ECD), and Vibrational Circular Dichroism (VCD). Computational prediction by Density Functional Theory (DFT) of VCD spectra and by Time-dependent DFT (TDDFT) of ORD and ECD spectra allowed to assign (7R,8R,10S) AC to naturally occurring (+)-inuloxin A. In the case of compound (−)-seiricardine A, which lacks useful for the analysis UV–Vis absorption, and thus provides a hardly detectable ECD spectrum and quite low ORD values, an introduction of a suitable chromophore by chemical derivatization was performed. The corresponding derivative, 2-O-p-bromobenzoate ester, gave rise to an intense ECD spectrum and higher ORD and VCD values. The comparison of computed spectra with the experimental ones allowed to assign (1S,2R,3aS,4S,5R,7aS) AC to (−)-2-O-p-bromobenzoate ester of seiricardine A and then to (−)-seiricardine A. This study further supports a recent trend of concerted application of more than a single chiroptical technique toward an unambiguous assignment of AC of flexible and complex natural products. Moreover, the use of chemical derivatization, with insertion of suitable chromophoric moieties has allowed to treat also UV–Vis transparent molecules by ECD and ORD spectroscopies.