Cathodic Regioselective Coupling of Unactivated Aliphatic Ketones with Alkenes.

A regioselective coupling of aliphatic ketones with alkenes has been realized by cathodic reduction. This reaction enables the formation of ketyl radicals and the activation of challenging alkenes under mild electrolysis conditions, providing an effective protocol for accessing diverse tertiary alcohols with substrate-dependent regioselectivity. The practicability of this reaction is demonstrated by scale-up experiments. The hydrogen source for the products, the migration isomerization of allylarenes, and the applicability of internal alkenes are demonstrated by control experiments.