Nickela‐electrocatalyzed C−H Alkoxylation with Secondary Alcohols: Oxidation‐Induced Reductive Elimination at Nickel(III)

Nickela‐electrooxidative C−H alkoxylations with challenging secondary alcohols were accomplished in a fully dehydrogenative fashion, thereby avoiding stoichiometric chemical oxidants, with H(2) as the only stoichiometric byproduct. The nickela‐electrocatalyzed oxygenation proved viable with various (hetero)arenes, including naturally occurring secondary alcohols, without racemization. Detailed mechanistic investigation, including DFT calculations and cyclovoltammetric studies of a well‐defined C−H activated nickel(III) intermediate, suggest an oxidation‐induced reductive elimination at nickel(III).