This study develops a biogenetic synthesis strategy using electrooxidation and heterodimerization of N-substituted pyrrolidine-1-carboxamides to create diverse analogues of the fissoldhimine alkaloid core. Under acidic conditions, 2-alkoxypyrrolidine-1-carboxamides from Shono oxidation formed endo-heterodimers with high yields and diastereoselectivity. Enantioselective heterodimerization using chiral phosphoric acid catalysis produced exo-heterodimers with high enantioselectivity.