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Type: Journal article
Title: Mechanistic studies on the autoxidation of α-guaiene: structural diversity of the sesquiterpenoid downstream products
Other Titles: Mechanistic studies on the autoxidation of alpha-guaiene: structural diversity of the sesquiterpenoid downstream products
Author: Huang, A.
Sefton, M.
Sumby, C.
Tiekink, E.
Taylor, D.
Citation: Journal of Natural Products, 2015; 78(1):131-145
Publisher: American Chemical Society
Issue Date: 2015
ISSN: 0163-3864
Statement of
An-Cheng Huang, Mark A. Sefton, Christopher J. Sumby, Edward R. T. Tiekink, and Dennis K. Taylor
Abstract: Two unstable hydroperoxides, 6b and 10a, and 13 downstream sesquiterpenoids have been isolated from the autoxidation mixture of the bicyclic sesquiterpene α-guaiene (1) on cellulose filter paper. One of the significant natural products isolated was rotundone (2), which is the only known impact odorant displaying a peppery aroma. Other products included corymbolone (4a) and its C-6 epimer 4b, the (2R)- and (2S)-rotundols (7a/b), and several hitherto unknown epimers of natural chabrolidione A, namely, 7-epi-chabrolidione A (3a) and 1,7-epi-chabrolidione A (3b). Two 4-hydroxyrotundones (8a/b) and a range of epoxides (9a/b and 5a/b) were also formed in significant amounts after autoxidation. Their structures were elucidated on the basis of spectroscopic data and X-ray crystallography, and a number of them were confirmed through total synthesis. The mechanisms of formation of the majority of the products may be accounted for by initial formation of the 2- and 4-hydroperoxyguaienes (6a/b and 10a/b) followed by various fragmentation or degradation pathways. Given that α-guaiene (1) is well known to exist in the essential oils of numerous plants, coupled with the fact that aerial oxidation to form this myriad of downstream oxidation products occurs readily at ambient temperature, suggests that many of them have been overlooked during previous isolation studies from natural sources.
Keywords: Sesquiterpenes
Sesquiterpenes, Guaiane
Crystallography, X-Ray
Molecular Structure
Hydrogen Peroxide
Rights: © 2015 The American Chemical Society and American Society of Pharmacognosy
DOI: 10.1021/np500819f
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