Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors

In this work, we report manganese porphyrin complexes for the electrocatalytic vicinal diazidation of alkenes with sodium azide. This protocol shows improved practicality over our previous work using MnBr2 catalysis in the following aspects: (1) it requires substantially lower catalyst loading (as low as 0.3 mol %), which reduces the formation of metal azide complexes and simplifies product purification; (2) the introduction of a neutral aqueous buffer prevents the generation of toxic hydrazoic acid, contributing to a safer experimental procedure; (3) the catalytic system displays improved reactivity toward unactivated terminal alkenes. Mechanistic studies support the roles of second-sphere hydrogen-bond donors in stabilizing key reaction intermediates.

Automated summary

This work presents manganese porphyrin complexes for the electrocatalytic vicinal diazidation of alkenes with sodium azide. Compared to previous studies using MnBr2 catalysis, this protocol shows improved practicality in terms of lower catalyst loading, enhanced safety measures, and increased reactivity towards unactivated terminal alkenes.