Electrochemical Cyanation of Alcohols Enabled by an Iodide-Mediated Phosphine P(V/III) Redox Couple

We report herein a mild electrochemical method to transform alcohols into their corresponding nitriles by using commercially available reagents. This protocol accepts substrates with various functional groups including those that are susceptible to oxidative decomposition. Mechanistic studies revealed a critical iodide-mediated phosphine electrochemical oxidation pathway leading to the alkoxyphosphonium intermediate, followed by nucleophilic substitution by a cyanide nucleophile. This method demonstrates the use of electrochemistry in replacing azo-type reagents in direct nucleophilic substitution and homologation of alcohol substrates.