Metal-Free and Visible Light-Induced Difunctionalizations of α-CF₃ Styrenes with Aryl Diazonium Salts and Hetero Nucleophiles

Metal-free, visible light-induced difunctionalizations of α-CF₃ styrenes with aryl diazonium salts and various hetero nucleophiles (ROH, H₂O, N₃⁻ and F⁻) are described. This concise protocol provided easy access to the α-CF₃ tertiary alkyl ethers, alcohol and fluorides with good yields and excellent functional group tolerance. In addition, the four-component “SO₂” insertion reaction also worked efficiently to produce the α-CF₃, β-sulfonyl ethers in moderate to good yields. A radical-polar crossover coupling pathway was proposed for the C−O bond formation.