Electrochemically Benzyl Cation‐Triggered Alkylacetoxylation of Terminal Alkynes and Carboxylic Acids

Abstract A catalyst‐free electrochemical alkylacetoxylation reaction of terminal alkynes with (thio)xanthenes and carboxylic acids is developed. Treating the addition products with K 2 CO 3 as a base in methanol affords the ketones in moderate to good yields. Preliminary experimental and computational studies indicate that the benzylic cation generated from the (thio)xanthenes triggers the electrophilic addition to alkynes.