Generation of Carbon Free Radicals by Reduction of the Cation Pool

The electrochemical reduction of N-acyliminium ions, which were generated by the “cation pool” method, led to the formation of carbon free radicals. Carbon radicals thus generated underwent homo-coupling reactions and the reactions with activated olefins, such as methyl acrylate. In the latter case, a mechanism involving the addition of a carbon radical to the carbon–carbon double bond, followed by one-electron reduction to give carbanions, has been proposed. The present study opens a new possibility for radical-mediated carbon–carbon bond formation based on the reduction of carbocations.