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Tautomerism and stereochemistry of dihydroxyperylenequinones: Force field investigations

Tautomerie und Stereochemie von Dihydroxyperylenchinonen: Untersuchungen mit Hilfe der Kraftfeld-Methodik

  • Organische Chemie Und Biochemie
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Summary

Stereochemistry and tautomerism of cercosporin and several of its partial structure models were investigated using an MM2 derived force field method. Besides the “propeller” type conformer, which was found before by X-ray crystallography, the complicated energy hypersurface was shown to contain a novel “double-butterfly” conformer of similar stability. The interconversion barrier between these conformers and their enantiomers was found to be unusually high due to buttressing effects of neighbor substituents. Judged from the calculations, the 4,9-tautomer of cercosporin could also be present in favoring instances besides the 3,10-tautomer, whereas the 3,9-tautomer is strongly destabilized.

Zusammenfassung

Die Stereochemie von Cercosporin und einigen seiner Partialstrukturmodelle wurde Hilfe einer von MM2 abgeleiteten Kraftfeldmethodik untersucht. In der komplizierten Energiehyperfläche wurde neben dem aus der Röntgenstrukturanalyse bekannten „Propeller“-Konformeren auch ein neues „Doppelschmetterling“-Konformer ähnlicher Stabilität aufgefunden. Die Interkonversionsbarrieren zwischen diesen Konformeren und ihren Enantiomeren sind außergewöhnlich hoch, was auf einen Buttressing-Effekt der benachbarten Substituenten zurückgeführt wurde. Aus den Rechnungen folgte auch, daß neben dem 3,10-Tautomeren in günstigen Fällen auch das 4,9-Tautomere des Cercosporins vorliegen kann, wogegen das 3,9-Tautomere stark destabilisiert ist.

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Authors and Affiliations

  1. Institut für Chemie, Johannes Kepler Universität Linz, A-4040, Linz, Austria

    Ch. Etzlstorfer, H. Falk & N. Müller

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  1. Ch. Etzlstorfer
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  2. H. Falk
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  3. N. Müller
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Etzlstorfer, C., Falk, H. & Müller, N. Tautomerism and stereochemistry of dihydroxyperylenequinones: Force field investigations. Monatsh Chem 124, 431–439 (1993). https://doi.org/10.1007/BF00814139

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  • DOI: https://doi.org/10.1007/BF00814139

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