Synthesis of phalluside-1 and Sch II using 1,2-metallate rearrangements.
(4E,8E,10E)-9-Methyl-4,8,10-sphingatrienine, a core component of marine sphingolipids, was synthesised for the first time using a copper(I)-mediated 1,2-metallate rearrangement of a lithiated glycal as a key step. It was converted to phalluside-1, a cerebroside isolated from the ascidian Phallusia fumigate. By an analogous route, (4E,8E)-9-methyl-4,8-sphingadiene was synthesised and converted to Sch II, a cerebroside that induces fruiting body formation in the basidiomycete Schizophyllum commune.
Black
Fiona J
FJ
School of Chemistry and Institute of Process Research and Development, Leeds University, Leeds, LS2 9JT, UK.
Kocienski
Philip J
PJ
D000818:Animals; D002554:Cerebrosides / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D012567:Schizophyllum / Q000737:chemistry*; D014561:Urochordata / Q000737:chemistry*
D002554:Cerebrosides