Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids.

Abstract

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis of alkenes with all substitution patterns has been accomplished by means of Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl acids as the limiting reagents and exhibit a broad scope with respect to both coupling partners. Notably, simple primary alkyl carboxylic acids could be readily engaged as carbon-centered radical precursors in the reaction. This new alkenylation protocol has been successfully demonstrated in direct modification of naturally occurring complex acids and is amenable to the enantioselective decarboxylative alkenylation of arylacetic acid. Mechanistic studies, including a series of controlled experiments and cyclic voltammetry data, allow us to probe the key intermediates and the pathway of the reaction.