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).