Electrocatalytic Oxidative Hydrofunctionalization Reactions of Alkenes via Co(II/III/IV) Cycle

Here we disclose a general and versatile Co(II/III/IV) electrocatalytic platform for alkene functionalization. Driven by electricity, a set of the oxidative hydrofunctionalization reactions initiated by hydrogen atom transfer were demonstrated without the need for stochiometric chemical oxidants. The scope of the reactions encompasses hydroalkoxylation, hydroacyloxylation, hydroarylation, semi-pinacol rearrangement, and deallylation. Mechanistic studies and stereochemical evidence support an ECEC process involving an electrochemically-generated organocobalt(IV) intermediate. This work presents an example of reactivity space expansion in electrocatalysis of VB12-systems by going beyond the common oxidation states of Co(I/II/III).