Organolithium-Mediated Conversion of β-Alkoxy Aziridines into Allylic Sulfonamides: Effect of the N-Sulfonyl Group and a Formal Synthesis of (±)-Perhydrohistrionicotoxin†

In 18 out of 20 examples of the organolithium-mediated conversion of β-alkoxy aziridines into substituted allylic sulfonamides, use of a Bus (Bus = t-BuSO2) substituent on the nitrogen gave higher yields compared to the analogous N-Ts compounds. The success with the N-Bus aziridines facilitated the development of a new route to the spirocyclic core of the histrionicotoxins and completion of a formal synthesis of (±)-perhydrohistrionicotoxin.