Metal‐Free Electrochemistry‐Driven Decarboxylative Primary Alkyl‐Alkoxylation of Olefins

Abstract Here, a primary alkylative difunctionalization of olefins based on the decarboxylation of carboxylate ions to obtain alkyl radicals by electrochemical anodic oxidation is reported. The reaction employs quaternary ammonium carboxylates as the source of alkyl radicals and does not require additional oxidizing agents or electrolytes. The reaction exhibits a broad substrate range and functional group compatibility. It gently converts mono‐ or disubstituted styrene substrates and alkyl carboxylate anions of various carbon chain lengths and substituents to products under the reaction conditions. Furthermore, it is important to note that not only alcohols but carboxylic acids and water can also serve as nucleophilic reagents to participate in the reaction and yield the corresponding products. Preliminary mechanistic studies have demonstrated that the reaction is enabled by the lower oxidation potential of the carboxylate anion compared to that of the olefin. The anodic oxidation of the carboxylate anion occurs prior to the oxidation of the olefin, followed by decarboxylation to obtain alkyl radicals.