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Synthetic and Isolation Studies Related to the Marine Natural Products (+)-Elisabethadione and (+)-Elisabethamine

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Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, Department of Chemistry and Biochemistry, Center of Excellence in Biomedical and Marine Biotechnology, Florida Atlantic University, Boca Raton, Florida 33431-0331, and Department of Chemistry, University of Prince Edward Island, Charlottetown, PEI, C1A-4P3, Canada
Cite this: J. Org. Chem. 2007, 72, 6, 1895–1900
Publication Date (Web):February 20, 2007
https://doi.org/10.1021/jo0618167
Copyright © 2007 American Chemical Society

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    Abstract

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    These studies were conducted to determine the discrepancies between the spectroscopic data of the isolated and synthetic samples of the marine natural product (+)-elisabethadione. Attempts at the re-isolation of (+)-elisabethadione from Pseudopterogorgia elisabethae were unsuccessful, but during these efforts, two related natural products of O-methylelisabethadione (8) and O-methyl-nor-elisabethadione (9) were discovered. The total syntheses of these new natural products were accomplished by using the combined C−H activation/Cope rearrangement as the key step and the previously synthesized elisabethadione was converted to O-methylelisabethadione. These studies confirmed that the synthetic sample of (+)-elisabthadione was assigned the correct structure. The considerable differences in the data between the synthetic and natural samples of (+)-elisabethadione lead to the conclusion that the structure of the natural material was either miss-assigned or the published spectral data were incorrect. During the course of these studies, questions arose about the assigned structure of another natural product, elisabethamine, which was proposed to be an aminohydroquinone. Attempts at the synthesis of this compound revealed that the aminohydroquinone structure was unstable in air as it was readily oxidized to the quinone.

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     University at Buffalo.

     Florida Atlantic University.

    §

     University of Prince Edward Island.

    *

     Address correspondence to this author. Phone:  +1-716-645-6800, ext 2186. Fax:  +1-716-645-6547.

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