The unprecedently rearranged 6/5/8/6/5 pentacyclic monoterpenoid indole alkaloid voafriamidine from Voacanga africana contains an uncommon N-acyl amidine structural motif that forms a unique 2,4-diazatricycle-[6,5,1(1,8),0(3,7)] tetradecane skeleton. Despite the lack of proper NMR correlations for the related quaternary carbon and nitrogen, the complex structure was finally elucidated by the combination of ACD/Structure Elucidator, density functional theory (DFT) calculations of the NMR spectra and electronic circular dichroism (ECD) analyses. (C) 2021 Elsevier Ltd. All rights reserved.