Summary
The diastereomericmono- andbis-ω-appended (R)-menthyl hypericin derivatives were studied by means of absorption spectroscopy, circular dichroism measurements, application of the C2 rule, and semiempirical calculations. This allowed us to assign the absolute configuration (P) to the inherently chiral phenanthroperylene quinone chromophore of hypericin, thebay-hypericinate ion, and the 1,6-dioxo-tautomer displaying a negativeCotton effect of their long wavelength absorption band. From these results and according to the positive chiroptical sign of their long wavelength bands, the absolute configuration (M) could be assigned to the stentorin chromophore in the native pigments.
Zusammenfassung
Die diastereomerenmono- undbis-ω-substituierten (R)-Menthyl-hypericinderivative wurden mit Hilfe der Absorptionsspektroskopie, von Circulardichroismusmessungen, der Anwendung der C2-Regel und semiempirischer Rechnungen untersucht. Dies erlaubte die Zuordnung der absoluten Konfiguration (P) für den inhärent chiralen Phenanthroperylenchinon-Chromophor von Hypericin, dasbay-Hypericination und das 1,6-Dioxotautomer, die einen negativenCotton-Effekt ihrer langwelligen Absorptionsbande aufweisen. Auf der Basis dieser Ergebnisse und aufgrund des positiven chiroptischen Signals seiner langwelligen Absorptionsbande wurde dem Stentorinchromophor in den nativen Pigmenten die absolute Konfiguration (M) zugeordnet.
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Altmann, R., Etzlstorfer, C. & Falk, H. Chiroptical properties and absolute configurations of the hypericin chromophore propeller enantiomers. Monatsh Chem 128, 785–793 (1997). https://doi.org/10.1007/BF00807089
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DOI: https://doi.org/10.1007/BF00807089