NMR-based determination of the configuration of complex molecules containing many stereocentersi so ften not possible using traditional NOE data and coupling patterns. Making use of residual dipolar couplings (RDCs), we were able to determine the relative configuration of an atural product containings even stereocenters, including a chiral aminel acking direct RDC data. To identify the correct relative configurationo ut of 32 possible ones, experimental RDCs were used in three different approaches for data interpretation:b yf itting experimental data based singularv alue decomposition(SVD) using as ingle alignment tensor and either (i)asingle conformer or (ii)multiple conformers,o ra l-ternatively (iii)using molecular dynamics simulations with tensorialo rientationalc onstraints (MDOC). Even thoughi n all three approaches one and the same configurationc ould be selected and clear discrimination betweenp ossible configurations was achieved, the experimentald ata was not fully satisfied by the methods based on single tensor approaches. While these two approaches are faster,o nly MDOCis able to fully reproduce experimental results, as the obtained conformational ensemble adequately coverst he conformational spacen ecessary to describe the molecule with inherent flexibility.