Hydrotrifluoromethylation and iodotrifluoromethylation of alkenes and alkynes using an inorganic electride as a radical generator

Abstract

The trifluoromethyl (CF3) group is a staple synthon that can alter the physical and chemical properties of organic molecules. Despite recent advances in trifluoromethylation methods, the development of a general synthetic methodology for efficient and selective trifluoromethylation remains an ongoing challenge motivated by a steadily increasing demand from the pharmaceutical, agrochemical and materials science industries. In this article, we describe a simple, efficient and environmentally benign strategy for the hydrotrifluoromethylation of unactivated alkenes and alkynes through a radical-mediated reaction using an inorganic electride, [Ca2N]þ e, as the electron source. In the transformation, anionic electrons are transferred from [Ca2N]þ e electrides to the trifluoromethylating reagent CF3I to initiate radical-mediated trifluoromethylation. The role of ethanol is pivotal in the transformation, acting as the solvent, an electron-releasing promoter and a hydrogen atom source. In addition, iodotrifluoromethylation of alkynes proceeds selectively upon the control of electride amount.