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 H2 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). II, III, or IV: Challenging secondary C−H alkoxygenations were accomplished with a versatile nickel electrocatalyst. Mechanistic investigation through isolation experiments, cyclovoltammetry, and density functional theory (DFT) calculations provided support for a process involving oxidation‐induced reductive elimination. MQ=6‐methylquinoline.