Mangana( iii / iv )electro-catalyzed C(sp 3 )–H azidation

Abstract

The merger of manganese-catalyzed C–H functionalization with electrosynthesis enabled C(sp 3 )–H azidation devoid of chemical oxidants or photochemical irradiation. Detailed mechanistic studies are supportive of a manganese( iii/iv ) electrocatalysis.

Manganaelectro-catalyzed azidation of otherwise inert C(sp 3 )–H bonds was accomplished using most user-friendly sodium azide as the nitrogen-source. The operationally simple, resource-economic C–H azidation strategy was characterized by mild reaction conditions, no directing group, traceless electrons as the sole redox-reagent, Earth-abundant manganese as the catalyst, high functional-group compatibility and high chemoselectivity, setting the stage for late-stage azidation of bioactive compounds. Detailed mechanistic studies by experiment, spectrophotometry and cyclic voltammetry provided strong support for metal-catalyzed aliphatic radical formation, along with subsequent azidyl radical transfer within a manganese( iii / iv ) manifold.