Electrochemical Radical Allylic Trifluoromethylation of Free Allylic Alcohols with Trifunctional Trifluoromethyl Thianthrenium Salts

The radical allylic substitution of free allylic alcohols remains a challenge. Herein, we report an electrochemical strategy that facilitates the dehydroxylative allylic trifluoromethylation of unprotected allylic alcohols with thianthrenium salts, affording trisubstituted alkenes with high regio- and <i>E</i>/<i>Z</i> selectivities. The key to this success lies in the electrochemical unlocking of the unique trifunctionality of thianthrenium salts, which serve synergistically as radical precursors, sacrificial anodic agents, and deoxygenation mediators.