A photometric screening method for dimeric naphthylisoquinoline alkaloids and complete on-line structural elucidation of a dimer in crude plant extracts, by the LC-MS/LC-NMR/LC-CD triad.
An efficient evaluation procedure for the chemical screening and on-line structural elucidation of dimeric naphthylisoquinoline alkaloids has been developed. The method is based on the lead tetraacetate oxidation of the central binaphthalene core of the alkaloids. UV spectra of the extracts after addition of the oxidant show, in the presence of naphthylisoquinoline dimers, the appearance of a characteristic long-wavelength absorption indicative of dinaphthoquinones. The efficiency and relevance of the method has been demonstrated in the discovery of a constitutionally and configurationally new dimeric naphthylisoquinoline alkaloid, named ancistrogriffithine A (4), from the previously uninvestigated Asian liana Ancistrocladus griffithii. After verification of this screening result by LC-ESI-MS/MS, the constitution and the relative configuration of the compound were elucidated on line, by LC-NMR and LC-CD on the extract. Using an LC-NMR-WET-ROESY experiment, itwas possible for the first time to determine the relative axial configuration of a natural biaryl compound on line, by observing long-range ROE interactions. Finally, an oxidative degradation right on the extract delivered the absolute configuration of 4, without isolation of the alkaloid. Ancistrogriffithine A is the as yet only dimeric naphthylisoquinoline from an Asian Ancistrocladaceae plant.
Bringmann
G
G
Institute of Organic Chemistry, University of Würzburg, Am Hubland, Germany. bringman@chemie.uni-wuerzburg.de
Wohlfarth
M
M
Rischer
H
H
Heubes
M
M
Saeb
W
W
Diem
S
S
Herderich
M
M
Schlauer
J
J
D000470:Alkaloids / Q000032:analysis* / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D002942:Circular Dichroism; D019281:Dimerization; D007546:Isoquinolines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D019684:Magnoliopsida / Q000737:chemistry*; D013058:Mass Spectrometry; D010936:Plant Extracts / Q000737:chemistry*; D018515:Plant Leaves / Q000737:chemistry
D000470:Alkaloids; D007546:Isoquinolines; D010936:Plant Extracts; C110299:ancistrobertsonine A