Enantiodivergent Biosynthesis of the Dimeric Sphingolipid Oceanapiside from the Marine Sponge Oceanapia phillipensis. Determination of Remote Stereochemistry

The absolute stereochemistry of oceanapiside, an antifungal α,ω-bis-aminohydroxylipid with four stereogenic centers from the marine sponge Oceanapia phillipensis Dendy, 1895, has been obtained as 2S,3R,26R,27R from development and application of a general CD method based on superposition of additive...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2000-05, Vol.122 (17), p.4011-4019
Main Authors: Nicholas, Gillian M, Molinski, Tadeusz F
Format: Article
Language:English
Subjects:
Oceanapia phillipensis
Oceanapiside
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Summary:The absolute stereochemistry of oceanapiside, an antifungal α,ω-bis-aminohydroxylipid with four stereogenic centers from the marine sponge Oceanapia phillipensis Dendy, 1895, has been obtained as 2S,3R,26R,27R from development and application of a general CD method based on superposition of additive exciton couplings in perbenzoyl derivatives of bis-amino alcohols. The method allows simultaneous determination of the local relative configuration at each of the termini of the long chain bis-aminolipid and also relates the absolute configuration of the two remote termini. Oceanapiside contains erythro and threo relative configurations at C1,2 and C26,27, respectively, but opposite absolute configurations at the amino substituted carbons C2 and C27 which implies an enantiodivergent biogenesis formally derived from both d- and l-amino acids.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja994215o