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Natural acetylenes. Part XVIII. Some allenic polyacetylenes from basidiomycetes
Journal of the Chemical Society C: Organic Pub Date : , DOI:10.1039/J39660000129
Abstract

The isolation, characterisation, and structure determination of ten polyacetylenes, including seven new allenic-diactylenes, from five Basidiomycete fungi (Cortinellus berkeleyanus, Odontia bicolor, Flammula sapinea, Daedalea juniperina, and the unidentified fungus B285) are described. The new allenic-diacetylenes are (a) HC[triple bond, length half m-dash]C·C[triple bond, length half m-dash]C·CH[double bond, length half m-dash]C[double bond, length half m-dash]CH·[CH2]n·OH (n= 1, 3, and 4); (b) HC[triple bond, length half m-dash]C·C[triple bond, length half m-dash]C·CH[double bond, length half m-dash]C[double bond, length half m-dash]CH·CH(OH)·[CH2]n·OH (n= 2 and 3); (c) HC[triple bond, length half m-dash]C·C[triple bond, length half m-dash]C·CH[double bond, length half m-dash]C[double bond, length half m-dash]CH·CH2·CH(OH)·CH2·CH2·OH; and (d) CH3·C[triple bond, length half m-dash]C·C[triple bond, length half m-dash]C·CH[double bond, length half m-dash]C[double bond, length half m-dash]CH·CH2·CH2·OH. The diols (b; n= 2) and (c) were conveniently purified and examined as their isopropylidene derivatives.

With the alcohols (a; n= 3 and 4), base-catalysed isomerisation, presumably intramolecularly assisted by the alkoxide anion, unexpectedly leads to disubstituted triacetylenic alcohols, CH3·(C[triple bond, length half m-dash]C)3·[CH2]n·OH. The sign of the very large optical rotations of these metabolities probably indicates the absolute configuration of the allene grouping.

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