Total Synthesis of (+)-Psychotrimine and Formal Synthesis of (+)-Psychotetramine via Late-Stage Ni(II)-Photoredox N-Arylation.

An efficient strategy for the total syntheses of architecturally complex alkaloids, (+)-psychotrimine (1), and formal synthesis of (+)-psychotetramine (2) has been achieved via late-stage Ni(II)-photoredox N-arylation. The method involves the formation of the key building blocks using mild indole addition to bromopyrroloindole and their assembly into the oligomeric hexahydropyrrolo[2,3-b]indole scaffolds via a blue LED-mediated metallaphotoredox-enabled C-N coupling reaction.