Herein, we describe the isolation, structure elucidation, and confirmatory biomimetic total synthesis of the first member of the paraherquamide/stephacidin family to possess the rare anti relative configuration within the bicyclo[2.2.2]diazaoctane ring system. We propose the new name of versicolamide B for this natural product (8), which is a minor metabolite of Aspergillus versicolor NRRL 35600. We have assigned the absolute configuration to this compound on the basis of the circular dichroism (CD) spectra, and have concluded that it possesses the ent configuration with respect to the bicyclo[2.2.2]diazaoctane core. Surprisingly, and just as striking, we have also isolated (-)-stephacidin A and (+)-notoamide B from Aspergillus versicolor NRRL 35600 and conclude that these natural products are produced as the corresponding enantiomers to the structures that have been previously described. The provocative biogenetic implications of these stereochemical findings are discussed herein.