Rhodaelectro‐Catalyzed peri‐Selective Direct Alkenylations with Weak O‐Coordination Enabled by the Hydrogen Evolution Reaction (HER)

Direct C−H functionalizations by electrocatalysis is dominated by strongly coordinating N(sp(2))‐directing groups. In sharp contrast, direct electrocatalytic transformations of weakly‐coordinating phenols remain underdeveloped. Herein, electrooxidative peri C−H alkenylations of challenging 1‐naphthols were achieved by versatile rhodium(III) catalysis via user‐friendly constant current electrolysis. The rhodaelectrocatalysis employed readily‐available alkenes and a protic reaction medium and features ample scope, good functional group tolerance and high site‐ and stereoselectivity. The strategy was successfully applied to high‐value, nitrogen‐containing heterocycles, thereby providing direct access to uncommon heterocyclic motifs based on the dihydropyranoquinoline skeleton.