Metal-free electrochemical anti-markovnikov hydration of aryl alkenes†

Abstract

The hydration of olefins is the most direct and effective method for producing alcohol molecules; however, it mainly proceeds with Markovnikov selectivity, and anti-Markovnikov hydration of olefins for the direct construction of primary alcohols remains challenging. Herein, we report a metal-free electrochemical anti-Markovnikov hydration of aryl alkenes, providing direct access to a wide spectrum of primary, secondary, and tertiary alcohols in moderate to high yields without the need for expensive transition metals or stoichiometric concentrations of chemical oxidants. Mechanistic experiments indicated that the reaction involves a collaborative electrooxidation of chloride ions at the anode and single-electron-transfer-induced reduction of epoxide at the cathode.