Ustilipids, acylated beta-D-mannopyranosyl D-erythritols from Ustilago maydis and Geotrichum candidum.
Ustilago species produce an extracellular oil that shows activity in various pharmaceutical assays. We isolated several complexes of this heterogeneous glycolipid from cultures of Ustilago maydis DSM 11494 and Geotrichum candidum ST 002515, and determined the chemical structures of these new compounds, termed ustilipids, on the basis of NMR experiments, mass spectra, and fatty acid analyses. They all possess a 4-O-beta-D-mannopyranosyl D-erythritol basic framework, the configuration of which was confirmed, after initial solvolysis, by a single-crystal X-ray structure analysis. All the investigated ustilipids and related compounds are similarly constructed: the three hydroxy groups of the erythritol side chain are free in all cases, whereas the hydroxy groups of the mannose residue are for the most part acylated. Medium-chain fatty acids have for the first time been detected as components of glycolipids produced by Ustilaginales. While the 2-hydroxy group of the mannose residue is esterified with a C2-C8 carboxylate side chain, the 3-hydroxy group is in all cases esterified by a longer, C12-C20 fatty acid residue. The oxygen functionalities at the 4 and 6 positions are either acetylated or present as free hydroxy groups. Ustilipids antagonize dopamine D3 receptors in micromolar quantities; other members of this class of compounds have been found to possess an inhibitory action on the neurotensin receptor. The hemolytic activity of ustilipids is low.
Kurz
Michael
M
Aventis Pharma Industriepark Höchst, D-65926 Frankfurt/Main, Germany. Michael.Kurz@aventis.com
Eder
Claudia
C
Isert
Dieter
D
Li
Ziyu
Z
Paulus
Erich F
EF
Schiell
Matthias
M
Toti
Luigi
L
Vértesy
Laszló
L
Wink
Joachim
J
Seibert
Gerhard
G
D002850:Chromatography, Gel; D002851:Chromatography, High Pressure Liquid; D018360:Crystallography, X-Ray; D018492:Dopamine Antagonists / Q000494:pharmacology; D004896:Erythritol / Q000031:analogs & derivatives*; D005227:Fatty Acids / Q000378:metabolism; D008401:Gas Chromatography-Mass Spectrometry; D005848:Geotrichum / Q000737:chemistry* / Q000378:metabolism; D006017:Glycolipids / Q000737:chemistry* / Q000302:isolation & purification / Q000494:pharmacology; D008968:Molecular Conformation; D019906:Nuclear Magnetic Resonance, Biomolecular; D018028:Receptors, Neurotensin / Q000037:antagonists & inhibitors; D014588:Ustilago / Q000737:chemistry* / Q000378:metabolism
D018492:Dopamine Antagonists; D005227:Fatty Acids; D006017:Glycolipids; D018028:Receptors, Neurotensin; D004896:Erythritol