Trifluoromethylation of Electron-Rich Alkenyl Iodides with Fluoroform-Derived "Ligandless" CuCF 3 .

We herein present a flexible approach for the incorporation of CF3 units into a predefined site of electron-rich alkenes that exploits the regiocontrolled introduction of an iodine handle and subsequent trifluoromethylation of the C(sp2 )-I bond using fluoroform-derived "ligandless" CuCF3 . The broad substrate scope and functional group tolerance together with the scalability and purity of the resulting products enabled the controlled, late-stage synthesis of single regioisomers of complex CF3 -scaffolds, such as sugars, nucleosides (antivirals), and heterocycles (indoles and chromones), with potential for academic and industrial applications.