Multi-Pathway Photochemical/Manganese-Catalyzed Diazidation of Alkenes

Abstract

Vicinal diamines, recognized for their attractive structural motifs and functional versatility, are widely used in pharmaceuticals, catalysis and functional materials. As the best choice, the diazidation of alkenes offers an efficient route for the rapid decoration of diazide compounds, which can be converted to the corresponding diamines via a simple reduction step. Although advanced strategies for alkene diazidation, primarily involving radical ligand transfer or a combination of radical ligand transfer and ligand-to-metal charge transfer, have been developed, most of the methods still face some limitations, such as the requirement for superstoichiometric oxidants, and notably differ substantially in substrate applicability. To address this shortcoming, we combine IBA-N₃ with in-situ generated Mn^II-N₃ to establish a synthetic strategy that can cover most of the different known pathways to incorporate the azide group into diazide compounds. Consequently, this protocol can significantly increase the suitable range of alkenes by overlapping multiple pathways to obtain azide sources. Mechanistic analysis indicates that this transformation strategy can include redox, photochemical homolysis of I^III-N₃, radical ligand transfer and radical group transfer processes to form a practical design to achieve alkene diazidation with a better scope of alkene tolerance.

Keywords

Diazidation / Alkene / Difunctionalization / Photochemical / Manganese-Catalyzed / Selectivity / LMCT

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