Herein, we describe the first total syntheses of five members of the dimeric nuphar alkaloids: (+)-6,6′-dihydroxythiobinupharidine (+)-1a, (+)-6-hydroxythiobinupharidine (+)-1b, (−)-6,6′-dihydroxythionuphlutine (−)-2a, (−)-6,6′-dihydroxyneothiobinupharidine (−)-3a, and (+)-6,6′-dihydroxyneothionuphlutine (+)-4a. The latter two have not been found in Nature. We have also made each of their enantiomers (−)-1a–b, (+)-2a, (+)-3a, and (−)-4a. The key step in these syntheses was the dimerization of an α-aminonitrile (a hydrolytically-stable surrogate for its corresponding hemiaminal) with chiral Lewis acid complexes. We have also reassigned the literature structures of (+)-1a–1b—for those instances in which the NMR spectra were obtained in CD3OD—to their corresponding CD3O– adducts. Our efforts provide for the first time apoptosis data for (−)-3a, (+)-4a, and all five non-natural antipodes prepared. The data indicate high apoptotic activity regardless of the enantiomer or relative stereochemical configuration at C7 and C7′.