Unambiguous assignments for free dimeric proanthocyanidin phenols from 2D NMR

• Published in: Phytochemistry (Oxford) 1996-09, Vol.43 (1), p.265-272
• Main Authors: de Bruyne, Tess, Pieters, Luc A.C., Dommisse, Roger A., Kolodziej, Herbert, Wray, Victor, Domke, Tobias, Vlietinck, Arnold J.
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Preparations and properties
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/0031-9422(96)00210-5

Characterization of proanthocyanidin oligomers proceeds commonly through investigation of NMR data of their peracetates or methyl ether acetates, in conjunction with FAB-mass spectrometry and circular dichroism. Since such an approach is unsuitable in bioassay-guided isolations, we applied two-dimensional NMR techniques for the identification of dimeric proanthocyanidins. This afforded not only a powerful probe for distinction between the different procyanidin isomers, but also allowed full assignments, even for both major rotameric forms, whenever present, without the need for derivatisation. Moreover, discrimination between the crucial 6- and 8-protons and carbons was achieved after addition of traces of cadmium nitrate, resulting in the separation of the broad phenolic signals into sharp singlets. As an example of the general strategy followed in the assignment and combination of data of the different spectra available, complete analysis of underivatised procyanidin B3 or catechin-(4α→8)-catechin is discussed for the first time.