Electrochemical trifluoromethylation of alkynes: the unique role of DMSO as a masking auxiliary

Abstract

Recent advancements in eco-friendly radical fluoroalkylation have substituted traditional two-electron-based reactions. However, the radical trifluoromethylation of terminal alkynes remains a significant challenge, primarily due to the high reactivity of alkenyl radical intermediates, which predominantly engage in reactions other than the desired elimination. In this work, we have developed an electrochemical trifluoromethylation method for terminal alkynes, facilitating the efficient formation of CF₃-alkynes. The success of this method centers on the use of DMSO as a “masking auxiliary”, which effectively stabilizes the alkenyl radical intermediate, allowing the reaction to proceed smoothly under mild conditions. This approach is supported by extensive experimental and computational studies, which elucidate the unique mechanism and expand the potential applications of radical trifluoromethylation across chemical synthesis.